Thienylpyrrole fungicidal agents

ABSTRACT

There are provided fungicidal thienyl- and furylpyrrole compounds of formula I ##STR1## Further provided are compositions and methods comprising those compounds for the protection of plants from fungal infestation and disease.

BACKGROUND OF THE INVENTION

Phytopathogenic fungi are the causal agents for many diseases thatinfect and destroy crops. In particular, the diseases apple scab, grapedowny mildew, wheat leaf rust and wheat powdery mildew are especiallydevastating.

In spite of the commercial fungicides available today, diseases causedby fungi still abound. Accordingly, there is ongoing research to createnew and more effective fungicides for controlling or preventing diseasescaused by phytopathogenic fungi.

Certain pyrrole compounds are known to possess acaricidal, fungicidal,insecticidal and/or antiinflammatory activity (see, e.g., U.S. Pat. Nos.4,267,184; 5,010,098; 5,102,904; 5,157,047 and 5,162,308, United Statespatent application Ser. Nos. 621,162 filed on Nov. 30, 1990; 803,289filed on Dec. 4, 1991; 966,990 filed on Oct. 27, 1992; 966,992 filed onOct. 27, 1992; 967,091 filed on October 27, 1992 and 971,025 filed onNovember 11, 1992, Japanese Patent Application JP-85-40874 filed on Mar.1, 1985, European Patent Application EP-111452-A1 filed on Jun. 20,1984, and N. Ono et al, Journal of Heterocyclic Chemistry, 28, pages2053-2055 (1991)). However, none of the pyrroles disclosed in thosepatents, patent applications and publication are within the scope of thepresent invention.

It is therefore an object of the present invention to provide a methodfor the prevention, control or amelioration of a disease caused by aphytopathogenic fungus.

It is also an object of the present invention to provide a method forthe protection of a plant, plant seed or tuber from fungal infestationand disease.

These and other objects of the present invention will become moreapparent from the detailed description thereof set forth below.

SUMMARY OF THE INVENTION

The present invention relates to a method for the prevention, control oramelioration of a disease caused by a phytopathogenic fungus bycontacting said fungus with a fungicidally effective amount of athienyl- or furylpyrrole compound having the following structuralformula I: ##STR2## wherein R, R₁ and R₂ are each independentlyhydrogen, halogen, NO₂ or CHO, and when R₁ and R₂ are taken togetherwith the carbon atoms to which they are attached, they may form a ringin which R₁ R₂ is represented by the structure: ##STR3## L, T, V and Ware each independently hydrogen, halogen, CN or NO₂ ; A is O or S;

X is CN, NO₂, C₁ -C₆ haloalkyl, S(O)_(m) CF₂ R₃ or C(S)NR₄ R₅ ;

R₃ is hydrogen, F, Cl, Br, CF₂ H, CCl₂ H, CClFH, CF₃ or CCl₃ ;

m is an integer of 0, 1 or 2;

R₄ and R₅ are each independently hydrogen,

C₁ -C₄ alkyl optionally substituted with one or more halogen atoms, orphenyl optionally substituted with one or more halogen atoms,

NO₂ groups,

CN groups,

C₁ -C₄ alkyl groups optionally substituted with one or more halogenatoms, or

C₁ -C₄ alkoxy groups optionally substituted with one or more halogenatoms;

Y is hydrogen, halogen, C₁ -C₆ haloalkyl, S(O)_(m) CF₂ R₃, CN or phenyloptionally substituted with one or more halogen atoms,

NO₂ groups,

CN groups,

C₁ -C₄ alkyl groups optionally substituted with one or more halogenatoms, or

C₁ -C₄ alkoxy groups optionally substituted

with one or more halogen atoms;

Z is hydrogen, halogen or C₁ -C₆ haloalkyl;

B is R₆, OR₆ or CN;

R₆ is hydrogen, C(O)R₇, CHR₈ NHC(O)R₉, CH₂ SQ, CHR₁₀ OC(O)(CR₁₁ R₁₂)_(n)Q₁,

C₁ -C₆ alkyl optionally substituted with one to three halogen atoms,

one tri(C₁ -C₄ alkyl)silyl,

one hydroxy,

one cyano,

one or two C₁ -C₄ alkoxy groups optionally substituted with one to threehalogen atoms,

one C₁ -C₄ alkylthio,

one phenyl optionally substituted with one to three halogen atoms, oneto three C₁ -C₄ alkyl groups or one to three C₁ -C₄ alkoxy groups,

one phenoxy group optionally substituted with one to three halogenatoms, one to three C₁ -C₄ alkyl groups or one to three C₁ -C₄ alkoxygroups,

one benzyloxy group optionally substituted on the phenyl ring with oneto three halogen atoms, one to three C₁ -C₄ alkyl groups or one to threeC₁ -C₄ alkoxy groups,

one C₁ -C₆ alkylcarbonyloxy group optionally substituted with one tothree halogen atoms,

one C₂ -C₆ alkenylcarbonyloxy group optionally substituted with one tothree halogen atoms,

one phenylcarbonyloxy group optionally substituted with one to threehalogen atoms, one to three C₁ -C₄ alkyl groups or one to three C₁ -C₄alkoxy groups,

one C₁ -C₆ alkoxycarbonyl group optionally substituted with one to threehalogen atoms or one to three C₁ -C₄ alkoxy groups, or

one benzylcarbonyloxy group optionally substituted on the phenyl ringwith one to three halogen atoms, one to three C₁ -C₄ alkyl groups or oneto three C₁ -C₄ alkoxy groups,

C₃ -C₆ alkenyl optionally substituted with one to three halogen atoms orone phenyl group, or

C₃ -C₆ alkynyl optionally substituted with one to three halogen atoms orone phenyl group;

R₇ is C₁ -C₆ alkyl or C₃ -C₆ cycloalkyl each optionally substituted withone to three halogen atoms,

one hydroxy,

one cyano,

one or two C₁ -C₄ alkoxy groups optionally substituted with one to threehalogen atoms,

one C₁ -C₄ alkylthio,

one phenyl group optionally substituted with one to three halogen atoms,

one to three C₁ -C₄ alkyl groups or

one to three C₁ -C₄ alkoxy groups,

one phenoxy group optionally substituted with one to three halogenatoms,

one to three C₁ -C₄ alkyl groups or

one to three C₁ -C₄ alkoxy groups,

one benzyloxy group optionally substituted on the phenyl ring with oneto three halogen atoms, one to three C₁ -C₄ alkyl groups or one to threeC₁ -C₄ alkoxy groups,

one C₁ -C₆ alkylcarbonyloxy group optionally substituted with one tothree halogen atoms,

one C₂ -C₆ alkenylcarbonyloxy group optionally substituted with one tothree halogen atoms,

one phenylcarbonyloxy group optionally substituted with one to threehalogen atoms, one to three C₁ -C₄ alkyl groups or one to three C₁ -C₄alkoxy groups,

one C₁ -C₆ alkoxycarbonyl group optionally substituted with one to threehalogen atoms or one to three C₁ -C₄ alkoxy groups, or

one benzyloxycarbonyl group optionally substituted on the phenyl ringwith one to three halogen atoms, one to three C₁ -C₄ alkyl groups or oneto three C₁ -C₄ alkoxy groups,

C₂ -C₆ alkenyl optionally substituted with one to three halogen atoms orone phenyl group,

C₃ -C₆ alkynyl optionally substituted with one to three halogen atoms orone phenyl group,

phenyl optionally substituted with one or more halogen atoms, C₁ -C₄alkyl groups, C₁ -C₄ alkoxy groups, phenoxy groups, C₁ -C₄ alkylthiogroups, tri(C₁ -C₄ alkyl)silyl groups, C₁ -C₄ alkylsulfinyl groups, C₁-C₄ alkylsulfonyl groups, CN groups, NO₂ groups or CF₃ groups,

phenoxy optionally substituted with one or more halogen atoms, C₁ -C₄alkyl groups, C₁ -C₄ alkoxy groups, C₁ -C₄ alkylthio groups, tri(C₁ -C₄alkyl)silyl groups, C₁ -C₄ alkylsulfinyl groups, C₁ -C₄ alkylsulfonylgroups, CN groups, NO₂ groups or CF₃ groups,

1- or 2-naphthyl,

2-, 3-, or 4-pyridyl optionally substituted with one to three halogenatoms,

C₁ -C₆ alkoxy optionally substituted with one to three halogen atoms, or

C₂ -C₆ alkenyloxy optionally substituted with one to three halogenatoms;

R₈ is hydrogen or C₁ -C₄ alkyl;

R₉ is C₁ -C₆ alkyl optionally substituted with one to three halogenatoms,

phenyl optionally substituted with one to three halogen atoms, CNgroups, NO₂ groups, C₁ -C₄ alkyl groups, C₁ -C₄ alkoxy groups or CF₃groups, 2- or 3-thienyl, or 2- or 3-furyl;

Q is ##STR4## CN, C₁ -C₆ alkyl optionally substituted with one or morehalogen atoms, CN groups or phenyl groups, or phenyl optionallysubstituted with one or more halogen atoms, C₁ -C₄ alkyl groups, C₁ -C₄alkoxy groups, CN groups, NO₂ groups, CF₃ groups or NR₂₄ R₂₅ groups;

A₁ is O or S;

R₁₃ is C₁ -C₆ alkyl or phenyl;

R₁₄ is C₁ -C₆ alkyl;

R₁₅ and R₁₆ are each independently hydrogen, C₁ -C₆ alkyl or may betaken together with the atom to which they are attached to form a 5- to7-membered ring;

R₁₇ is C₁ -C₄ alkyl;

R₁₈ is hydrogen, C₁ -C₄ alkyl or may be taken together with either R₁₉or R₂₁ and the atoms to which they are attached to form a 5- to7-membered ring optionally substituted with one or two C₁ -C₄ alkylgroups;

R₁₉ and R₂₀ are each independently hydrogen or C₁ -C₄ alkyl;

R₂₁ is C₁ -C₄ alkyl or when taken together with R₁₈ and the atoms towhich they are attached may form a 5- to 7-membered ring optionallysubstituted with one or two C₁ -C₄ alkyl groups;

R₂₂ and R₂₃ are each independently hydrogen or C₁ -C₄ alkyl or whentaken together may form a ring wherein R₂₂ R₂₃ is represented by--CH═CH--CH═CH--;

R₂₄ and R₂₅ are each independently hydrogen or C₁ -C₄ alkyl;

R₁₀ is hydrogen or C₁ -C₄ alkyl;

R₁₁ and R₁₂ are each independently hydrogen,

C₁ -C₆ alkyl optionally substituted with one or more halogen atoms,

C₁ -C₆ alkoxy optionally substituted with one or more halogen atoms,

C₁ -C₆ alkylthio optionally substituted with one or more halogen atoms,or phenyl optionally substituted with one or more halogen atoms,

NO₂ groups;

CN groups,

C₁ -C₄ alkyl groups optionally substituted with one or more halogenatoms, or

C₁ -C₄ alkoxy groups optionally substituted with one or more halogenatoms, or

when R₁₁ and R₁₂ are taken together with the atom to which they areattached may form a C₃ -C₆ cycloalkyl group optionally substituted withone to three C₁ -C₄ alkyl groups, C₂ -C₆ alkenyl groups or phenylgroups, or R₁₁ or R₁₂ may be taken together with R₂₆ and the atoms towhich they are attached to form a 4- to 7-membered heterocyclic ring;

n is an integer of 0, 1, 2, 3 or 4;

Q₁ is A₂ R₂₆, ##STR5## NR₂₈ R₂₉, CR₃₀ R₃₁ C(O)R₃₂, or C₃ -C₆ cycloalkyloptionally substituted with one or more C₁ -C₆ alkyl groups,

C₂ -C₆ alkenyl groups, or phenyl groups optionally substituted with oneor more halogen atoms,

NO₂ groups,

CN groups,

C₁ -C₄ alkyl groups optionally substituted with one or more halogenatoms, or

C₁ -C₄ alkoxy groups optionally substituted with one or more halogenatoms;

A₂ is O or S(O)_(p) ;

p is an integer of 0, 1 or 2;

R₂₆ is hydrogen,

C₁ -C₆ alkyl

C₂ -C₆ alkenyl,

C₂ -C₆ alkynyl,

phenyl optionally substituted with one or more halogen atoms,

NO₂ groups,

CN groups,

C₁ -C₄ alkyl groups optionally substituted with one or more halogenatoms, or

C₁ -C₄ alkoxy groups optionally substituted with one or more halogenatoms,

C(O)R₃₃ provided p is O,

C(O)R₃₄ provided p is O,

(CH₂ CH₂ O)_(q) R₃₃, or ##STR6## R₂₆ may be taken together with eitherR₁₁ or R₁₂ and the atoms to which they are attached to form a 4- to7-membered heterocyclic ring;

A₃ is O or S;

R₃₃ is C₁ -C₆ alkyl,

C₂ -C₆ alkenyl,

C₂ -C₆ alkynyl, or phenyl optionally substituted with one or morehalogen atoms,

NO₂ groups,

CN groups,

C₁ -C₄ alkyl groups optionally substituted with one or more halogenatoms, or

C₁ -C₄ alkoxy groups optionally substituted with one or more halogenatoms;

q is an integer of 1, 2 or 3;

R₃₄ is OR₃₇ or NR₃₈ R₃₉ ;

R₃₇ is C₁ -C₆ alkyl or phenyl optionally substituted with one or morehalogen atoms,

NO₂ groups,

CN groups,

C₁ -C₄ alkyl groups optionally substituted with one or more halogenatoms, or

C₁ -C₄ alkoxy groups optionally substituted with one or more halogenatoms;

R₃₈ and R₃₉ are each independently hydrogen or C₁ -C₄ alkyl;

R₃₅ and R₃₆ are each independently hydrogen or C₁ -C₄ alkyl, or whentaken together may form a ring wherein R₃₅ R₃₆ is represented by--CH═CH--CH═CH--;

R₂₇ is C₁ -C₄ alkyl;

R₂₈ is hydrogen,

C₁ -C₆ alkyl,

C₂ -C₆ alkenyl,

C₂ -C₆ alkynyl, or

phenyl optionally substituted with one or more halogen atoms,

NO₂ groups,

CN groups,

C₁ -C₄ alkyl groups optionally substituted with one or more halogenatoms, or

C₁ -C₄ alkoxy groups optionally substituted with one or more halogenatoms, or

R₂₈ may be taken together with either R₁₁ or R₁₂ and the atoms to whichthey are attached to form a 4- to 7-membered heterocyclic ring;

R₂₉ is hydrogen,

C₁ -C₆ alkyl,

C₂ -C₆ alkenyl,

C₂ -C₆ alkynyl,

phenyl optionally substituted with one or more halogen atoms,

NO₂ groups,

CN groups,

C₁ -C₄ alkyl groups optionally substituted with one or more halogenatoms, or

C₁ -C₄ alkoxy groups optionally substituted with one or more halogenatoms,

C(A₄)R₄₀,

CN,

SO₂ R₄₁, or

C(O)CHR₄₂ NHR₄₃ ;

A₄ is O or S;

R₄₀ is OR₄₄, CO₂ R₄₄, NR₄₅ R₄₆,

C₁ -C₆ alkyl optionally substituted with one to three halogen atoms,

C₂ -C₆ alkenyl,

C₂ -C₆ alkynyl, or

phenyl optionally substituted with one or more halogen atoms,

NO₂ groups,

CN groups,

C₁ -C₄ alkyl groups optionally substituted with one or more halogenatoms, or

C₁ -C₄ alkoxy groups optionally substituted with one or more halogenatoms;

R₄₄ is C₁ -C₆ alkyl optionally substituted with one phenyl group, or

phenyl optionally substituted with one or more halogen atoms,

NO₂ groups,

CN groups,

C₁ -C₄ alkyl groups optionally substituted with one or more halogenatoms, or

C₁ -C₄ alkoxy groups optionally substituted with one or more halogenatoms;

R₄₅ and R₄₆ are each independently hydrogen or C₁ -C₄ alkyl;

R₄₁ is NR₄₇ R₄₈,

C₁ -C₆ alkyl,

C₂ -C₆ alkenyl,

C₂ -C₆ alkynyl, or

phenyl optionally substituted with one or more halogen atoms,

NO₂ groups,

CN groups,

C₁ -C₄ alkyl groups optionally substituted with one or more halogenatoms, or

C₁ -C₄ alkoxy groups optionally substituted with one or more halogenatoms;

R₄₇ and R₄₈ are each independently hydrogen or C₁ -C₄ alkyl;

R₄₂ is hydrogen,

C₁ -C₄ alkyl optionally substituted with one hydroxy group,

one SR₄₉ group,

one C(O)NH₂ group,

one NH₂ group,

one NHC(═NH)NH₂ group,

one CO₂ H group,

one phenyl group optionally substituted with one hydroxy group,

one 3-indolyl group or

one 4-imidazolyl group;

R₄₉ is hydrogen or C₁ -C₄ alkyl;

R₄₃ is C(A₄)R₅₀ ;

R₅₀ is C₁ -C₆ alkyl optionally substituted with one or more halogenatoms,

C₁ -C₆ alkoxyalkyl,

C₁ -C₆ alkylthio,

phenyl optionally substituted with one or more halogen atoms,

NO₂ groups,

CN groups,

C₁ -C₄ alkyl groups optionally substituted with one or more halogenatoms, or

C₁ -C₄ alkoxy groups optionally substituted with one or more halogenatoms,

OR₄₄,

CO₂ R₄₄ or

NR₄₅ R₄₆ ;

R₃₀ and R₃₁ are each independently hydrogen,

C₁ -C₆ alkyl optionally substituted with one or more halogen atoms,

C₁ -C₆ alkoxy optionally substituted with one or more halogen atoms,

C₁ -C₆ alkylthio optionally substituted with one or more halogen atoms,

phenyl optionally substituted with one or more halogen atoms,

CN groups,

NO₂ groups,

C₁ -C₄ alkyl groups optionally substituted with one or more halogenatoms, or

C₁ -C₄ alkoxy groups optionally substituted with one or more halogenatoms, or

when R₃₀ and R₃₁ are taken together with the atom to which they areattached may form a C₃ -C₆ cycloalkyl group optionally substituted withone to three C₁ -C₄ alkyl groups, C₂ -C₆ alkenyl groups or phenylgroups;

R₃₂ is OR₅₁, NR₄₇ R₄₈, C₁ -C₄ alkyl or phenyl optionally substitutedwith one or more halogen atoms,

CN groups,

NO₂ groups,

C₁ -C₄ alkyl groups optionally substituted with one or more halogenatoms, or

C₁ -C₄ alkoxy groups optionally substituted with one or more halogenatoms; and

R₅₁ is C₁ -C₄ alkyl or phenyl optionally substituted with one or morehalogen atoms,

CN groups,

NO₂ groups,

C₁ -C₄ alkyl groups optionally substituted with one or more halogenatoms, or

C₁ -C₄ alkoxy groups optionally substituted with one or more halogenatoms;

provided that when A is S, X is S(O)_(m) CF₂ R₃ and Z is hydrogen, thenY is hydrogen, halogen, C₁ -C₆ haloalkyl, S(O)_(m) CF₂ R₃ or CN; andfurther provided that when the pyrrole ring is substituted with hydrogenat each of the pyrrole carbon atoms adjacent to the ring nitrogen atom,then X cannot be CN or NO₂.

This invention also relates to a method for the protection of a plant,plant seed or tuber from fungal infestation and disease.

DETAILED DESCRIPTION OF THE INVENTION

Phytopathogenic fungi are the causal agents for many diseases thatinfect and destroy agronomic crops, both growing and harvested. In theUnited States alone, agronomic crops must compete with about 18,000species of fungi. Especially devastating are diseases such as applescab, grape downy mildew, wheat leaf rust, wheat powdery mildew and thelike. Accordingly, there is ongoing research to create new and moreeffective fungicides for preventing or controlling the vast array offungal infestations of crops.

Advantageously, the present invention provides a method for theprevention, control or amelioration of a disease caused by aphytopathogenic fungus by contacting said fungus with a fungicidallyeffective amount of a formula I thienyl- or furylpyrrole compound.

The present invention also provides a method for the protection of aplant, plant seed or tuber from fungal infestation and disease byapplying to the plant, plant seed or tuber, or to the medium or water inwhich it is growing, a fungicidally effective amount of a formula Ithienyl- or furylpyrrole compound.

The term "medium" used herein is defined as any environment, includingbut not limited to artificial nutrients or soil, in which a plant can bekept, live or thrive.

The fungicidal thienyl- and furylpyrrole compounds of this inventionhave the following structural formula I: ##STR7## wherein R, R₁, R₂, A,X, Y, Z and B are as described hereinabove for formula I.

Preferred formula I thienyl- and furylpyrrole fungicidal agents of thepresent invention are those wherein

R, R₁ and R₂ are each independently hydrogen, halogen or NO₂, and whenR₁ and R₂ are taken together with the carbon atoms to which they areattached, they may form a ring in which R₁ R₂ is represented by thestructure: ##STR8## L, T, V and W are each independently hydrogen,halogen, CN or NO₂ ; A is O or S;

X is CN, NO₂, C₁ -C₆ haloalkyl, S(O)_(m) CF₂ R₃ or C(S)NR₄ R₅ ;

R₃ is hydrogen, F, Cl, Br, CF₂ H, CCl₂ H, CClFH, CF₃ or CCl₃ ;

m is an integer of 0, 1 or 2;

R₄ and R₅ are each independently hydrogen,

C₁ -C₄ alkyl optionally substituted with one or more halogen atoms, or

phenyl optionally substituted with one or more halogen atoms,

NO₂ groups,

CN groups,

C₁ -C₄ alkyl groups optionally substituted with one or more halogenatoms, or

C₁ -C₄ alkoxy groups optionally substituted with one or more halogenatoms;

Y is hydrogen, halogen, C₁ -C₆ haloalkyl, S(O)_(m) CF₂ R₃, CN or

phenyl optionally substituted with one or more halogen atoms,

NO₂ groups,

CN groups,

C₁ -C₄ alkyl groups optionally substituted with one or more halogenatoms, or

C₁ -C₄ alkoxy groups optionally substituted with one or more halogenatoms;

Z is hydrogen, halogen or C₁ -C₆ haloalkyl;

B is R₆ or CN;

R₆ is hydrogen, C(O)R₇, or

C₁ -C₆ alkyl optionally substituted with one to three halogen atoms,

one cyano,

one C₁ -C₄ alkoxy group,

one C₁ -C₆ alkylcarbonyloxy group,

one phenylcarbonyloxy group, or

one benzylcarbonyloxy group; and

R₇ is phenyl optionally substituted with one or more halogen atoms, C₁-C₄ alkyl groups, C₁ -C₄ alkoxy groups, CN groups, NO₂ groups or CF₃groups.

Another group of preferred formula I fungicidal agents are those wherein

R, R₁ and R₂ are each independently hydrogen, halogen or NO₂, and whenR₁ and R₂ are taken together with the carbon atoms to which they areattached, they may form a ring in which R₁ R₂ is represented by thestructure: ##STR9## L, T, V and W are each independently hydrogen,halogen, CN or NO₂ ; A is O or S;

X is CN, NO₂ or C₁ -C₆ haloalkyl;

Y is hydrogen, halogen, C₁ -C₆ haloalkyl or phenyl optionallysubstituted with one or more halogen atoms,

NO₂ groups,

CN groups,

C₁ -C₄ alkyl groups optionally substituted with one or more halogenatoms, or

C₁ -C₄ alkoxy groups optionally substituted with one or more halogenatoms;

Z is hydrogen, halogen or C₁ -C₆ haloalkyl;

B is R₆ or CN;

R₆ is hydrogen, C(O)R₇ or

C₁ -C₆ alkyl optionally substituted with one to three halogen atoms,

one cyano,

one C₁ -C₄ alkoxy group,

one C₁ -C₆ alkylcarbonyloxy group,

one phenylcarbonyloxy group, or

one benzylcarbonyloxy group; and

R₇ is phenyl optionally substituted with one or more halogen atoms, C₁-C₄ alkyl groups, C₁ -C₄ alkoxy groups, CN groups, NO₂ groups or CF₃groups.

More preferred formula I thienyl- and furylpyrrole fungicidal agents ofthis invention are those wherein

R, R₁ and R₂ are each independently hydrogen, halogen or NO₂, and whenR₁ and R₂ are taken together with the carbon atoms to which they areattached, they may form a ring in which R₁ R₂ is represented by thestructure: ##STR10## L, T, V and W are each independently hydrogen,halogen, CN or NO₂ ; A is O or S;

X is CN, NO₂ or C₁ -C₆ haloalkyl;

Y is hydrogen, halogen, C₁ -C₆ haloalkyl or phenyl optionallysubstituted with one or more halogen atoms,

NO₂ groups,

CN groups,

C₁ -C₄ alkyl groups optionally substituted with one or more halogenatoms, or

C₁ -C₄ alkoxy groups optionally substituted with one or more halogenatoms;

Z is halogen or C₁ -C₆ haloalkyl;

B is R₆ or CN;

R₆ is hydrogen, C(O)R₇ or

C₁ -C₆ alkyl optionally substituted with one to three halogen atoms,

one cyano,

one C₁ -C₄ alkoxy group,

one C₁ -C₆ alkylcarbonyloxy group,

one phenylcarbonyloxy group, or

one benzylcarbonyloxy group; and

R₇ is phenyl optionally substituted with one or more halogen atoms, C₁-C₄ alkyl groups, C₁ -C₄ alkoxy groups, CN groups, NO₂ groups or CF₃groups.

Another group of more preferred formula I thienyl- and furylpyrrolefungicidal agents are those wherein

R, R₁ and R₂ are each independently hydrogen, halogen or NO₂, and whenR₁ and R₂ are taken together with the carbon atoms to which they areattached, they may form a ring in which R₁ R₂ is represented by thestructure: --CH═CH--CH═CH--;

A is O or S;

X is CN or NO₂ ;

Y is halogen, CF₃ or

phenyl optionally substituted with one or more halogen atoms,

NO₂ groups,

CN groups,

C₁ -C₄ alkyl groups optionally substituted with one or more halogenatoms, or

C₁ -C₄ alkoxy groups optionally substituted with one or more halogenatoms;

Z is hydrogen, halogen or CF₃ ; and

B is hydrogen or C₁ -C₆ alkyl substituted with one C₁ -C₄ alkoxy group.

Most preferred formula I fungicidal agents are those wherein

R, R₁ and R₂ are each independently hydrogen, halogen or NO₂ ;

A is O or S;

X is CN or NO₂ ;

Y is halogen, CF₃ or phenyl optionally substituted with one or morehalogen atoms,

NO₂ groups,

CN groups,

C₁ -C₄ alkyl groups optionally substituted with one or more halogenatoms, or

C₁ -C₄ alkoxy groups optionally substituted with one or more halogenatoms;

Z is CF₃ ; and

B is hydrogen or C₁ -C₆ alkyl substituted with one C₁ -C₄ alkoxy group.

Exemplary of halogen hereinabove are fluorine, chlorine, bromine andiodine. The term "C₁ -C₆ haloalkyl" is defined as a C₁ -C₆ alkyl groupsubstituted with one or more halogen atoms.

Advantageously, it has been found that the formula I fungicidal agentsof the present invention are useful in the prevention, control oramelioration of diseases such as apple scab, grape downy mildew, wheatleaf rust and wheat powdery mildew. Such diseases are caused by thephytopathogenic fungi Venturia inaequalis, Plasmopara viticola, Pucciniarecondita f. sp. tritici and Erysiphe graminis f. sp. tritici,respectively.

Thienyl- and furylpyrrole compounds of formula I wherein X is CN and Y,Z and B are hydrogen. may be prepapred by reacting an N-formyl(thienylor furyl)glycine of formula II with 2-chloroacrylonitrile and aceticanhydride as shown in Flow Diagram I. ##STR11##

Certain compounds of formula I wherein X is CN, Y is C₁ -C₆ haloalkyland Z and B are hydrogen may be prepared by reacting the appropriatelysubstituted thienyl- or furylglycine of formula III with a C₁ -C₆haloalkyl acid anhydride to form an oxazolinone intermediate of formulaIV and reacting said formula IV intermediate with 2-chloroacrylonitrileas shown in Flow Diagram II. ##STR12##

Formula I compounds wherein X and Y are C₁ -C₆ haloalkyl and Z and B arehydrogen may be prepared by reacting an oxazolinone of formula IV with abromoalkene of formula V as shown in Flow Diagram III. ##STR13##

4-Cyano-2-(thienyl- or furyl)pyrrole compounds may be prepared byreacting acrylonitrile with anN-(trimethylsilyl)methyl-5-methyl-(thienyl- or furyl)thioimidate offormula VI in the presence of tetrabutylammonium fluoride to form a2-(thienyl- or furyl)-1-pyrroline-4-carbonitrile intermediate of formulaVII and reacting said formula VII intermediate with2,3-dichloro-5,6-dicyano-1,4-benzoquinone and pyridine as shown below inFlow Diagram IV. ##STR14##

3-Cyano or nitro-2-thienylpyrrole compounds may be prepared as shownbelow in Flow Diagram V. ##STR15## wherein R, R₁ and R₂ are eachindependently hydrogen, halogen or NO₂, and when R₁ and R₂ are takentogether with the carbon atoms to which they are attached, they may forma ring in which R₁ R₂ is represented by the structure: ##STR16## L, T, Vand W are each independently hydrogen, halogen, CN or NO₂ ; X is CN orNO₂ ; and

R₅₂ is C₁ -C₄ alkyl.

2-(Thienyl- or furyl)pyrrole-3,4-dicarbonitrile compounds may beprepared as shown below in Flow Diagram VI. ##STR17##

Formula I compounds wherein X is C(S)NH₂ may be prepared by reacting theappropriately substituted formula VIII (thienyl- orfuryl)pyrrole-carbonitrile with an excess of hydrogen peroxide andsodium hydroxide to give the appropriately substituted formula IX(thienyl- or furyl)pyrrole carboxamide and reacting said formula IXcarboxamide with a reagent capable of introducing the thioxo group, suchas 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfideas shown below in Flow Diagram VII. ##STR18## wherein A, B, Y and Z areas described hereinabove for formula I;

R, R₁ and R₂ are each independently hydrogen, halogen or NO₂, and whenR₁ and R₂ are taken together with the carbon atoms to which they areattached, they may form a ring in which R₁ R₂ is represented by thestructure: ##STR19## L, T, V and W are each independently hydrogen,halogen, CN or NO₂.

4- (Thienyl- or furyl) pyrrole-3-thiocarboxamide compounds may beprepared by reacting the appropriately substituted formula X aldehydewith triethyl phosphonoacetate, lithium chloride and triethylamine toform the ester of formula XI. The formula XI ester is reacted with astrong base such as sodium hydride and tosylmethyl isocyanide to form aformula XII ethyl 4-(thienyl- or furyl) pyrrole-3-carboxylate which ishydrolyzed with an alkali metal hydroxide such as potassium hydroxide toform a formula XIII 4-(thienyl- or furyl)pyrrole-3-carboxylic acid. Theformula XIII carboxylic acid is reacted with a tri(C₁ -C₄ alkyl)amine toform a first mixture. The first mixture is reacted with thionyl chlorideand N,N-dimethylformamide to give a second mixture. The second mixtureis reacted with a formula XIV amine compound to give the formula XV4-(thienyl- or furyl)pyrrole-3-carboxamide and reacting the formula XVcarboxamide with a reagent capable of introducing the thioxo group, suchas 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide,to give the desired 4-(thienyl- or furyl)pyrrole-3-thiocarboxamide. Theabove reaction schemes are shown below in Flow Diagram VIII. ##STR20##wherein A, R₄ and R₅ are as described hereinabove for formula I;

R, R₁ and R₂ are each independently hydrogen, halogen or NO₂, and whenR₁ and R₂ are taken together with the carbon atoms to which they areattached, they may form a ring in which R₁ R₂ is represented by thestructure: ##STR21## L, T, V and W are each independently hydrogen,halogen, CN or NO₂.

2-(Thienyl- and furyl)-1-hydroxypyrrole-3-carbonitrile compounds may beprepared by reacting a formula XVI ester with an acetal ofcyanopropionaldehyde in the presence of sodium hydride to form an acetalof formula XVII and reacting the formula XVII acetal with hydroxylaminehydrochloride as shown in Flow Diagram IX. ##STR22## wherein A is O orS;

R, R₁ and R₂ are each independently hydrogen, halogen or NO₂, and whenR₁ and R₂ are taken together with the carbon atoms to which they areattached, they may form a ring in which R₁ R₂ is represented by thestructure: ##STR23## L, T, V and W are each independently hydrogen,halogen, CN or NO₂.

5-(Thienylpyrrole-2,3-dicarbonitrile compounds of formula I may beprepared by reacting a formula XVIII oxime with sodium oxalacetate toform a formula XIX intermediate which is reacted with hydrochloric acidin the presence of an alcohol to form a formula XX5-thienyl-1-hydroxypyrrole-3-carboxylate. The formula XX carboxylate isreacted with methyl iodide and potassium t-butoxide to give a formulaXXI 5-thienyl-1-methoxypyrrole-3-carboxylate. Saponification of theformula XXI carboxylate gives a formula XXII5-thienyl-1-methoxypyrrole-3-carboxylic acid which is reacted withchlorosulfonyl isocyanate and N,N-dimethylformamide to give the formulaI 5-thienylpyrrole-2,3-dicarbonitrile. The above reaction scheme isshown in Flow Diagram X. ##STR24## wherein R, R₁ and R₂ are eachindependently hydrogen, halogen or NO₂, and when R₁ and R₂ are takentogether with the carbon atoms to which they are attached, they may forma ring in which R₁ R₂ is represented by the structure: ##STR25## L, T, Vand W are each independently hydrogen, halogen, CN or NO₂ ; and

R₅₃ is C₁ -C₆ alkyl or C₃ -C₆ cycloalkyl.

2,4-Dibromo-5-(2-thienyl)-1-methoxypyrrole-3-carbonitrile compounds ofthe present invention may 15 be prepared by reacting a formula XXIII5-(2-thienyl)-1-methoxypyrrole-3-carboxylate with bromine to form aformula XXIV 2,4-dibromo-5-(2-thienyl)-1-methoxypyrrole-3-carboxylate.Saponification of the formula XXIV carboxylate gives a formula XXV acidwhich is reacted with chlorosulfonyl isocyanate and dimethylformamide togive the desired2,4-dibromo-5-(2-thienyl)-1-methoxypyrrole-3-carbonitrile. The abovereaction scheme is shown in Flow Diagram XI. ##STR26## wherein R and R₁are each independently hydrogen, halogen or NO₂, and when R₁ is takentogether with R₂ and the carbon atoms to which they are attached, theymay form a ring in which R₁ R₂ is represented by the structure:##STR27## R₂ is halogen, and when taken together with R₁ and the carbonatoms to which they are attached, they may form a ring in which R₁ R₂ isrepresented by the structure: ##STR28## L, T, V and W are eachindependently hydrogen, halogen, CN or NO₂ ; and

R₅₃ is C₁ -C₆ alkyl or C₃ -C₆ cycloalkyl.

Similarly, 2,4-dibromo-5-(3-thienyl)-1-methoxypyrrole-3-carbonitrilecompounds may be prepared as shown in Flow Diagram XII. ##STR29##wherein R₁ is hydrogen, halogen or NO₂, and when R₁ is taken togetherwith R₂ and the carbon atoms to which they are attached, they may form aring in which R₁ R₂ is represented by the structure: ##STR30## R and R₂are each independently halogen, and when R₂ is taken together with R₁and the carbon atoms to which they are attached, they may form a ring inwhich R₁ R₂ is represented by the structure: ##STR31## L, T, V and W areeach independently hydrogen, halogen, CN or NO₂ ; and

R₅₃ is C₁ -C₆ alkyl or C₃ -C₆ cycloalkyl. 4-Bromo-2-(C₁ -C₆haloalkyl)-5-(2-thienyl)-1-methoxypyrrole-3-carbonitrile compounds ofthe present invention may be prepared as shown in Flow Diagram XIII.##STR32## wherein Y is C₁ -C₆ haloalkyl and R, R₁, R₂ and R₅₃ are asdescribed in Flow Diagram XI.

Similarly, 4-bromo-2-(C₁ -C₆haloalkyl)-5-(3-thienyl)-1-methoxypyrrole-3-carbonitrile compounds maybe prepared as shown in Flow Diagram XIV. ##STR33## wherein Y is C₁ -C₆haloalkyl and R, R₁, R₂ and R₅₃ are as described in Flow Diagram XII.

3,4-Dibromo-5-(2-thienyl)-1-methoxypyrrole-2-carbonitrile compounds maybe prepared by reacting a 5-(2-thienyl)-1-methoxypyrrole-3-carboxylatewith chlorosulfonyl isocyanate and dimethylformamide to give a2-cyano-5-(2-thienyl)-1-methoxypyrrole-3-carboxylate. Saponification andbromination of the 2-cyano-5-(2-thienyl)-1-methoxypyrrole-3-carboxylatecompound gives the desired3,4-dibromo-5-(2-thienyl)-1-methoxypyrrole-2-carbonitrile as shown inFlow Diagram XV. ##STR34## wherein R, R₁, R₂ and R₅₃ are as described inFlow Diagram XI.

Similarly, 3,4-dibromo-5-(3-thienyl)-1-methoxypyrrole-2-carbonitrilecompounds may be prepared as shown in Flow Diagram XVI. ##STR35##wherein R, R₁, R₂ and R₅₃ are as described in Flow Diagram XII.

Formula I 2-bromo-3-nitro-5-(C₁ -C₆haloalkyl)-4-(2-thienyl)-1-methoxypyrrole compounds may be prepared asshown in Flow Diagram XVII. ##STR36## wherein Y is C₁ -C₆ haloalkyl andR, R₁, R₂ and R₅₃ are as described in Flow Diagram XI.

Similarly, 2-bromo-3-nitro-5- (C₁ -C₆haloalkyl)-4-(3-thienyl)-1-methoxypyrrole compounds may be prepared asshown in Flow Diagram XVIII. ##STR37## wherein Y is C₁ -C₆ haloalkyl andR, R₁, R₂ and R₅₃ are as described in Flow Diagram XII.

3-Bromo-5-(C₁ -C₆haloalkyl)-4-(2-thienyl)-1-methoxypyrrole-2-carbonitrile compounds maybe prepared as shown in Flow Diagram XIX. ##STR38## wherein Y is C₁ -C₆haloalkyl and R, R₁, R₂ and R₅₃ are as described in Flow Diagram XI.

Similarly, 3-bromo-5-(C₁ -C₆haloalkyl)-4-(3-thienyl)-1-methoxypyrrole-2-carbonitrile compounds maybe prepared as shown in Flow Diagram XX. ##STR39## wherein Y is C₁ -C₆haloalkyl and R, R₁, R₂ and R₅₃ are as described in Flow Diagram XII.

4-Aryl-3-(nitro and cyano)-5-(C₁ -C₆ haloalkyl)-2-(2- and 3-thienyl and-furyl)pyrrole compounds may be prepared by reacting a substituted orunsubstituted beta-(nitro or cyano)styrene of formula XXVI with bromineto form a (substituted or unsubstituted-phenyl)-1,2-dibromo-2-(nitro orcyano)ethane of formula XXVII which is then subjected to adehalogenation treatment using a base such as pyridine to form asubstituted or unsubstituted (nitro or cyano)bromostyrene of formulaXXVIII. Reaction of the bromostryrene with a formula XXIX oxazolinone inthe presence of a tri(C₁ -C₄ alkyl)amine gives the desired4-aryl-3-(nitro or cyano)-5-(C₁ -C₆ haloalkyl)-2-(2- or 3-thienyl or-furyl)pyrrole. The above reaction scheme is shown in Flow Diagram XXI.##STR40## wherein X is CN or NO₂ ;

Y is phenyl optionally substituted with one or more halogen atoms,

NO₂ groups,

CN groups,

C₁ -C₄ alkyl groups optionally substituted with one or more halogenatoms, or

C₁ -C₄ alkoxy groups optionally substituted with one or more halogenatoms;

Z is C₁ -C₆ haloalkyl;

A is O or S;

R, R₁ and R₂ are each independently hydrogen, halogen or NO₂, and whenR₁ and R₂ are taken together with the carbon atoms to which they areattached, they may form a ring in which R₁ R₂ is represented by thestructure: ##STR41## L, T, V and W are each independently hydrogen,halogen, CN or NO₂.

Similarly, 4-(2-thienyl and -furyl)-3-(nitro and cyano)-5-(C₁ -C₆haloalkyl)-2-arylpyrrole compounds may be prepared as shown in FlowDiagram XXII and 4-(3-thienyl and -furyl)-3-(nitro and cyano)-5-(C₁ -C₆haloalkyl)-2-arylpyrrole compounds may be prepared as shown in FlowDiagram XXIII. ##STR42## wherein A, X, Y and Z are as described in FlowDiagram XXI and R, R₁ and R₂ are as described in Flow Diagram XI.##STR43## wherein A, X, Y and Z are as described in Flow Diagram XXI andR, R₁ and R₂ are as described in Flow Diagram XII.

3-Aryl-2-(C₁ -C₆ haloalkyl)-5-(2- and 3-thienyl and -furyl)pyrrolecompounds may be prepared as shown in Flow Diagram XXIV. ##STR44##wherein Y, Z, A, R, R₁ and R₂ are as described in Flow Diagram XXI.

Similarly, 3-(2- and 3-thienyl and -furyl)-2-(C₁ -C₆haloalkyl)-5-arylpyrrole compounds may be prepared as shown in FlowDiagram XXV. ##STR45## wherein Y, Z, A, R, R₁ and R₂ are as described inFlow Diagram XXI.

5-(C₁ -C₆ Haloalkyl)-3-aryl-2-(2- and 3-thienyl and -furyl)pyrrolecompounds may be prepared by reacting a substituted or unsubstitutedacetophenone of formula XXX with a thionyl halide in the presence of anorganic base such as pyridine. Thereafter, the reaction mixture istreated with aqueous sodium tetrafluoroborate to give a formula XXXIN-α-(substituted or unsubstituted)styrylpyridinium tetrafluoroborate.The formula XXXI styrylpyridinium tetrafluoroborate is then reacted witha formula XXIX oxazolinone in the presence of a base, such as pyridineto form the desired 5-(C₁ -C₆ haloalkyl)-3-aryl-2-(2- or 3-thienyl or-furyl)pyrrole compound. The above reaction scheme is shown in FlowDiagram XXVI. ##STR46## wherein Y, Z, A, R, R₁ and R₂ are as describedin Flow Diagram XXI.

Similarly, 5-(C₁ -C₆ haloalkyl)-2-aryl-3-(2-thienyl and -furyl)pyrrolecompounds may be prepared as shown in Flow Diagram XXVII and 5-(C₁ -C₆haloalkyl)-2-aryl-3-(3-thienyl and -furyl)pyrrole compounds may beprepared as shown in Flow Diagram XXVIII. ##STR47## wherein A, Z and Yare as described in Flow Diagram XXI and R, R₁ and R₂ are as describedin Flow Diagram XI. ##STR48## wherein A, Z and Y are as described inFlow Diagram XXI and R, R₁ and R₂ are as described in Flow Diagram XII.

5-(C₁ -C₆ haloalkyl)-2-aryl-4-nitro-3-(2-thienyl)pyrrole compounds maybe prepared by reacting a 5-(C₁ -C₆haloalkyl)-2-aryl-3-(2-thienyl)pyrrole compound with nitric acid andacetic anhydride as shown in Flow Diagram XXIX. ##STR49## wherein A, Zand Y are as described in Flow Diagram XXI and R, R₁ and R₂ are asdescribed in Flow Diagram XI.

Similarly, 5-(C₁ -C₆ haloalkyl)-2-aryl-4-nitro-3-(3-thienyl)pyrrolecompounds may be prepared as shown in Flow Diagram XXX. ##STR50##wherein A, Z and Y are as described in Flow Diagram XXI and R, R₁ and R₂are as described in Flow Diagram XII.

2,3,5-Tris(trifluoromethyl)-4-(2- and 3-thienyl)pyrrole compounds of thepresent invention may be prepared by reacting a formula XXX 3-(2- or3-thienyl-1,1,1-trifluoro-2-propanone with hydroxylamine hydrochlorideto form a formula XXXI oxime. The formula XXXI oxime is then reacted ina pressure bottle with liquid hexafluoro-2-butyne in the presence of atleast a ten mole percent amount of a base such as an alkali metalalkoxide in a solvent at an elevated temperature to form a formula XXXII3-(2- or3-thienyl)-5a-hydroxy-2,4-a,5b-tris(trifluoromethyl)-1-pyrroline. Theformula XXXII pyrroline is then reacted with hydrochloric acid in analcohol to form the desired 2,3,5-tris(trifluoromethyl)-4-(2- or3-thienyl)pyrrole compound. The above reaction scheme is shown in FlowDiagram XXXI. ##STR51##

3,4-Bis(trifluoromethyl)-2-(2- and 3-thienyl and -furyl)pyrrolecompounds may be prepared by reacting anN-(trimethylsilyl)methyl-5-methyl(thienyl- or furyl)thioimidate offormula VI with 2,3-dichlorohexafluorobutene as shown below in FlowDiagram XXXII. ##STR52##

2,3-Bis(trifluoromethyl)-4-halo-5-(2-thienyl)pyrrole compounds may beprepared by reacting an oxime of formula XXXIII with hexafluoro-2-butynein the presence of a base such as an alkali metal alkoxide to form thevinyl oxime of formula XXXIV and the2-(2-thienyl)-4,5-trans-bis(trifluoromethyl)-1-pyrrolin-5-ol of formulaXXXV. The formula XXXIV vinyl oxime is then heated to form the formulaXXXVI 2-(2-thienyl-4,5-bis(trifluoromethyl)-1-pyrrolin-4-ol. The formulaXXXV pyrrolin-5-ol or formula XXXVI pyrrolin-4-ol is then reacted withhydrochloric acid in an alcohol to obtain a5-(2-thienyl)-2,3-bis(trifluoromethyl)pyrrole compound. The5-(2-thienyl)-2,3-bis(trifluoromethyl)pyrrole is then reacted with ahalogenating agent to obtain the desired2,3-bis(trifluoromethyl)-4-halo-5-(2-thienyl)pyrrole. The above reactionscheme is shown in Flow Diagram XXXIII. ##STR53## wherein X is Cl, Br orI and R, R₁ and R₂ are as described in Flow Diagram XI.

Similarly, 2,3-Bis(trifluoromethyl)-4-halo-5-(3-thienyl)pyrrolecompounds may be prepared as shown in Flow Diagram XXXIV. ##STR54##wherein X is Cl, Br or I and R, R₁ and R₂ are as described in FlowDiagram XII.

2,5-Bis(trifluoromethyl)-3-(2- and 3thienyl)pyrrole compounds may beprepared as shown in Flow Diagram XXXV. ##STR55##

3-(Haloalkylsulfonyl)-2-(2- and 3-thienyl)pyrrole compounds may beprepared by reacting a (2- or 3-thienyl)ethynyl haloalkylsulfonylcompound of formula XXXVII with an aminoacetaldehyde di(C₁ -C₄alkyl)acetal to form a {{α-[(haloalkylsulfonyl)methylene](2- or3-thienyl)}amino}acetaldehyde di(C₁ -C₄ alkyl)acetal of formula XXXVIII.The formula XXXVIII acetal is then reacted with excess trifluoroaceticacid to obtain the desired 3-(haloalkylsulfonyl)-2-(2- or3-thienyl)pyrrole compound. The above reaction scheme is shown in FlowDiagram XXXVI. ##STR56##

5-(Haloalkylthio)-2-(2- and 3-thienyl and -furyl)pyrrole compounds maybe prepared by reacting a 2-(2- or 3-thienyl or -furyl)pyrrole compoundwith a haloalkylsulfenyl chloride compound in the presence of a base asshown in Flow Diagram XXXVII. ##STR57##

4-(Haloalkylsulfonyl)-5-(2-thenyl)pyrrole-2-carbonitrile compounds maybe prepared by reacting a 3-(haloalkylsulfonyl)-2-(2-thienyl)pyrrolecompound of formula XXXIX with chlorosulfonyl isocyanate in the presenceof a solvent to form a reaction mixture. The reaction mixture is thentreated with dimethylformamide to obtain the desired4-(haloalkylsulfonyl)-5-(2-thienyl)pyrrole-2-carbonitrile compound. Theabove reaction scheme is shown in Flow Diagram XXXVIII. ##STR58##wherein R₃ is as described above for formula I and R, R₁ and R₂ areasdescribed in Flow Diagram XI.

Similarly, 4-(haloalkylsulfonyl)-5-(3-thienyl)pyrrole-2-carbonitrilecompounds may be prepared as shown in Flow Diagram XXXIX. ##STR59##wherein R₃ is as described above for formula I and R, R₁ and R₂ are asdescribed in Flow Diagram XII.

5-(Haloalkylsulfinyl)-2-(2- and 3-thienyl and -furyl)pyrrole compoundsmay be prepared by reacting a 5-(haloalkylthio)-2-(2- or 3-thienyl or-furyl)pyrrole compound with an oxidizing agent such as3-chloroperoxybenzoic acid as shown in Flow Diagram XL. ##STR60##wherein A and R₃ are as described above for formula I; R, R₁ and R₂ areas described in Flow Diagram V and Y and Z are each independentlyhydrogen or halogen.

3-(2-And 3-thienyl and -furyl)-4-(haloalkylsulfonyl)pyrrole compoundsmay be prepared by reacting a haloalkylsulfone of formula XL withN-methylene-1-(p-tolylsulfonyl)methylamine in the presence of a basesuch as sodium hydride as shown in Flow Diagram XLI. ##STR61##

2-(Thienyl and furyl)-3-nitro-5-(haloalkylthio)pyrrole compounds and5-(thienyl and furyl)-3-nitro-2-(haloalkylthio)pyrrole compounds may beprepared by reacting a 2-(thienyl or furyl)-5-(haloalkylthio)pyrrolecompound with fuming nitric acid in the presence of acetic anhydride asshown in Flow Diagram XLII. ##STR62## wherein A and R₃ are as describedabove for formula I and R, R₁ and R₂ are halogen.

Similarly, 2-(2-thienyl)-5-nitro-3-(haloalkylsulfonyl)pyrrole compoundsand 2-(3-thienyl)-5-nitro-3-(haloalkylsulfonyl)pyrrole compounds may beprepared as shown in Flow Diagrams XLIII and XLIV, respectively.##STR63## wherein A and R₃ are as described above for formula I and R,R₁ and R₂ are as described in Flow Diagram XI. ##STR64## wherein A andR₃ are as described above for formula I and R, R₁ and R₂ are asdescribed in Flow Diagram XII.

Methods for preparing 2-(2-thienyl)-3-(haloalkylthio)pyrrole compoundsand 2-(3-thienyl)-3-(haloalkylthio)pyrrole compounds are shown in FlowDiagrams XLV and XLVI, respectively. ##STR65## wherein R, R₁ and R₂ areas described in Flow Diagram XI. ##STR66## wherein R, R₁ and R₂ are asdescribed in Flow Diagram XII.

3-Bromo-5-(thienyl or furyl)-2-(haloalkylsulfinyl and-sulfonyl-4-(haloalkylsulfonyl)pyrrole compounds may be prepared asshown in Flow Diagrams XLVII and XLVIII. ##STR67## wherein A and R areas described above for formula I and R, R₁ and R₂ are as described inFlow Diagram XI., ##STR68## wherein A and R are as described above forformula I and R, R₁ and R₂ are as described in Flow Diagram XII.

2-(Thienyl and furyl)-4-aryl-5-haloalkyl-3-(haloalkylsulfonyl)pyrrolecompounds may be prepared as shown in Flow Diagram XLIX. ##STR69##wherein A, R, R₁, R₂, Y and Z are as described in Flow Diagram XXI andR₃ is as described above for formula I.

Similarly, 2-aryl-4-(thienyl andfuryl)-5-haloalkyl-3-(haloalkylsulfonyl)pyrrole compounds may beprepared as shown in Flow Diagram L. ##STR70## wherein A, R, R₁, R₂, Yand Z are as described in Flow Diagram XXI and R₃ is as described abovefor formula I.

2-(Thienyl and furyl)-5-(haloalkylsulfonyl)pyrrole-3-carbonitrilecompounds may be prepared as shown in Flow Diagram LI. ##STR71##

Conversion of formula I compounds wherein Y and/or Z are hydrogen to thecorresponding formula I compounds wherein Y and/or Z are halogen isreadily achieved by reaction of the formula I hydrogen substitutedpyrrole with at least about 1 or 2 equivalents of a halogenating agentsuch as a sulfuryl halide, bromine or chlorine in the presence of asolvent such as dioxane, tetrahydroforan, acetic acid or a chlorinatedhydrocarbon solvent. In addition, formula I compounds wherein R, R₁and/or R₂ are hydrogen may be converted to the corresponding formula Icompounds wherein R, R₁ and/or R₂ are halogen by reaction of the formulaI compound wherein R, R₁ and/or R₂ are hydrogen with a halogenatingagent in the presence of a solvent. Halogenating agents that may beemployed include bromine, sulfuryl chloride, sulfuryl bromide, sodiumhypochlorite, t-butylhypochlorite, N-bromosuccinimide, N-iodosuccinimideand the like. Several halogenation reaction schemes are shown in FlowDiagram LII. ##STR72##

Preparation of 1-substituted formula I compounds can be achieved byreaction of the appropriately substituted formula I compound having B ashydrogen with an alkylating or acylating agent in the presence of analkai metal alkoxide or hydride. For example, a formula I compoundwherein B is hydrogen and R, R₁, R₂, A, X, Y and Z are as described forformula I above, is reacted with an appropriate alkylating agent such asa C₁ -C₆ alkylhalide in which the alkyl group is straight or branchedand is optionally substituted with from one to three halogen atoms, onehydroxy, one cyano, one C₁ -C₄ alkoxy, one C₁ -C₄ alkylthio, one phenylgroup optionally substituted with from one to three halogen atoms, orone benzyloxy group optionally substituted with from one to threehalogen atoms, and an alkali metal alkoxide such as sodium or potassiumt-butoxide. This reaction provides a thienyl- or furylpyrrole having thesame substituents as the starting material, but in addition issubstituted on the nitrogen with a C₁ -C₆ alkyl group optionallysubstituted as described above. This reaction scheme may be illustratedas follows: ##STR73## wherein R, R₁, R₂, A, X, Y and Z are as describedfor formula I above and R₆ is C₁ -C₆ alkyl optionally substituted asdescribed above. In a similar reaction cyanogen bromide is substitutedfor the alkylhalide and yields a formula I thienyl- or furylpyrrolehaving a carbonitrile, rather than an alkyl group on the 1-position.

Advantageously, the above-described alkylation procedure may also beapplied to the preparation of formula I thienyl- and furylpyrroleshaving an N-C₃ -C₆ alkenyl or N-C₃ -C₆ alkynyl substituent. Thissubstitution is obtained by simply substituting a C₃ -C₆ alkenyl halideor C₃ -C₆ alkynyl halide for the C₁ -C₆ alkyl halide in theabove-described reaction.

In a similar manner, preparation of 1-acylated thienyl- andfurylpyrroles may be achieved by the reaction of an appropriatelysubstituted formula I thienyl- or furylpyrrole wherein B is hydrogenwith an acylating agent in the presence of an alkali metal alkoxide.Acylating agents such as C₁ -C₆ alkyl or C₂ -C₆ alkenyl acid chlorides,substituted C₁ -C₆ alkyl or C₂ -C₆ alkenyl acid chlorides, benzoylchloride, substituted benzoyl chlorides, phenylchloroformate,substituted phenylchloroformates, C₁ -C₆ alkyl or C₂ -C₆alkenylchloroformates, substituted C₁ -C₆ alkyl or C₂ -C₆alkenylchloroformates, N-substituted carbamoyl chlorides and the likemay be employed. The reaction may be illustrated as follows: ##STR74##

Formula I thienyl- and furylpyrroles wherein R₆ is CH₂ SQ may beprepared by reaction of the appropriately substituted formula I thienyl-or furylpyrrole having R₆ as chloromethyl with an alkali metal salt ofan SQ compound in the presence of a base. And formula I thienyl- andfurylpyrrole compounds wherein R₆ is CHR₈ NHC(O)R₉ may be prepared ashown below. ##STR75##

Advantageously, 1-halomethyl thienyl- and furylpyrroles may be preparedas shown below. ##STR76##

Formula I compounds wherein R₆ is R₁₀ CHOC(O)(CR₁₁ R₁₂)_(n) Q₁ may beprepared as shown below. ##STR77##

Formula I compounds wherein B is OR₆ may be prepared by reacting anappropriately substituted formula I thienyl- or furylpyrrole compound,wherein B is OH, and R, R₁, R₂, A, X, Y and Z are as described forformula I above, with an appropriate alkylating agent and a suitablebase, for example, a chloromethyl C₁ -C₄ alkyl ether and potassiumt-butoxide. This reaction provides a thienyl- or furylpyrrole having thesame substituents as the starting material, but in addition issubstituted on the oxygen with C₁ -C₄ alkoxymethyl. In a similarreaction bromoacetonitrile is substituted for the chloromethyl C₁ -C₄alkyl ether and gives a formula I thienyl- or furylpyrrole with anacetonitrile substituent on the oxygen. The reactions may be illustratedas follows: ##STR78## wherein R, R₁, R₂, A, X, Y and Z are as describedfor formula I above and R₆ is (1) C₁ -C₄ alkoxymethyl or (2) CH₂ CN.

Similarly, formula I compounds wherein B is C(O)R₇ may be prepared byreacting an appropriately substituted formula I thienyl- or furylpyrrolecompound, wherein B is OH, and R, R₁, R₂, A, X, Y and Z are as describedfor formula I above, with an appropriate acylating agent and a suitablebase, for example, a C₁ -C₆ acid chloride and potassium t-butoxide. Thisreaction provides a thienyl- or furylpyrrole compound having the samesubstituents as the starting material, but in addition is substituted onthe oxygen with C₁ -C₆ alkanoyl. The reaction may be illustrated asfollows: ##STR79##

The formula I compounds of this invention are especially useful forcontrolling or preventing the growth of phytopathogenic fungi such asVenturia inaequalis, Plasmopara viticola, Puccinia recondita f. sp.tritici and Erysiphe graminis f. sp. tritici. Therefore, harmfuldiseases such as apple scab, grape downy mildew, wheat leaf rust andwheat powdery mildew may be prevented or controlled.

The thienyl- and furylpyrrole compounds of the present invention arealso useful for the protection of growing or harvested plants from thedamage caused by phytopathogenic fungal disease when applied to saidplants at a fungicidally effective rate. The effective rate will varydepending upon factors such as the virulence of the target fungus, theenvironment of the treatment and other ambient conditions. In practice,generally about 20 ppm to 1,000 ppm, preferably about 50 ppm to 500 ppmof a formula I thienyl- or furylpyrrole compound may be dispersed in aliquid or solid carrier and applied to the plant, seed or tuber, or tothe medium or water in which the plant, seed or tuber is growing.

The formula I fungicidal compounds of the invention may be formulated asconcentrated solutions, emulsifiable concentrates, flowableconcentrates, microemulsions and the like. Said compounds may also beformulated as dry compacted granules, granular compositions, dusts, dustconcentrates, suspension concentrates, wettable powders, and the like.Those formulations which lend themselves to seed, tuber, medium, waterand/or foliage applications to provide the requisite plant protectionare suitable. Such formulations include the fungicidal compounds of theinvention admixed with an inert solid or liquid carrier.

It is contemplated that the fungicidal compounds of the invention may beused in conjunction with, or in combination with, a pesticidallyeffective amount of one or more other pesticides, including but notlimited to, anilazine, benalaxyl, benomyl, bitertanol, bordeaux mixture,carbendazim, carboxin, captafol, captan, chlorothalonil, cyproconazole,dichloran, diethofencarb, diniconazole, dithianon, dodine, edifenphos,fenarimol, fenbuconazole, fenfuram, fenpropidin, fenpropimorph, fentinhydroxide, ferbam, flusilazole, flusulfamide, flutriafol, folpet,fosetyl, fuberidazole, guazatine, hexaconazole, imazalil, iprobenfos,iprodione, mancozeb, maneb, metalaxyl, metiram, myclobutanil, nuarimol,ofurace, oxadixyl, oxycarboxin, penconazole, probenazole, prochloraz,propiconazole, pyrazophos, tebuconazole, thiabendazole, thiophanate,thiophanate-methyl, triadimefon, triadimenol, triarimol, tricyclazole,tridemorph, triflumizole, triforine, vinclozolin, and/or zineb.

Where compositions of the invention are to be employed in combinationtreatments with other pesticidal agents, the composition may be appliedconcurrently as an admixture of the components as described above, ormay be applied sequentially.

In order to facilitate a further understanding of the invention, thefollowing examples are presented primarily for the purpose ofillustrating more specific details thereof. The examples generallyutilize the above reation schemes and also provide further means forpreparing even more compounds of the present invention which are notspecifically described above. The invention should not be deemed limitedby the examples as the full scope of the invention is defined in theclaims.

EXAMPLE 1 Preparation of 3,4,5-Trichloro-2-Thiophenecarboxaldehyde##STR80##

Butyllithium (2.5 molar in tetrahydrofuran, 3.96 mL, 9.9 mmol) is addedto a solution of tetrachlorothiophene (2.00 g, 9.01 mmol) intetrahydrofuran at 0° C. The reaction mixture is stirred at 0° C. for 30minutes, warmed to room temperature over 45 minutes, treated withN,N-dimethylformamide (0.79 g, 10.8 mmol), stirred for three hours,poured into one molar hydrochloric acid at 4° C. and extracted withether. The combined organic extracts are washed sequentially with waterand brine, dried over MgSO₄ and concentrated in vacuo to obtain a brownsolid. Flash chromatography of the solid using silica gel and a 5% ethylacetate in hexane solution gives a beige solid which is recrystallizedfrom ethyl acetate and hexane to obtain the title product as beigeneedles (1.63 g, 84%, mp 81°-82° C.).

EXAMPLE 2 Preparation of the Oxime of3,4,5-Trichloro-2-Thiophenecarboxaldehyde ##STR81##

A solution of sodium carbonate (10.91 g, 99.2 mmol) in water is added toa slurry of 3,4,5-trichloro-2-thiophenecarboxaldehyde (10.69 g, 49.6mmol) and hydroxylamine sulfate (8.14 g, 49.6 mmol) in water. Afterstirring at room temperature for 18 hours, the solids are filtered outof the reaction mixture and dried under high vacuum overnight to givethe title product as a white solid (10.24 g, 92%).

Using essentially the same procedure, and employing the appropriatelysubstituted thiophenecarboxaldehyde, the following compounds areobtained.

    ______________________________________                                        R           R.sub.1   R.sub.2                                                 ______________________________________                                         ##STR82##                                                                    H           H         Cl                                                      H           Br        H                                                       H           CHCHCHCH                                                           ##STR83##                                                                    H           H         H                                                       ______________________________________                                    

EXAMPLE 3 Preparation of 3,4,5-Trichloro-2-Thiophenecarbonitrile##STR84##

A solution of the oxime of 3,4,5-trichloro-2-thiophenecarboxaldehyde(10.08 g, 43.7 mmol) in acetic anhydride is refluxed for two hours andconcentrated in vacuo to obtain a brown oil. The oil is diluted withether and the organic solution is washed sequentially with water andbrine, dried over MgSO₄ and concentrated in vacuo to give a brown oil.Flash chromatography of the oil using silica gel and a 5% ethyl acetatein hexane solution gives a beige solid which is recrystallized fromethyl acetate and hexane to obtain the title product as beige needles(8.23 g, 89%, mp 63°-64° C.).

Using essentially the same procedure, and employing the appropriatelysubstituted oxime, the following compounds are obtained:

    ______________________________________                                        R           R.sub.1   R.sub.2                                                 ______________________________________                                         ##STR85##                                                                    H           H         Cl                                                      H           Br        H                                                       H           CHCHCHCH                                                           ##STR86##                                                                    H           H         H                                                       ______________________________________                                    

EXAMPLE 4 Preparation of2-(3,4,5-Trichloro-2-Thienyl)-5-(Trifluoromethyl)Pyrrole-3-Carbonitrile##STR87##

Acetonitrile (0.97 g, 23.7 mmol) is added dropwise to a solution oflithium diisopropylamide (two molar in hydrocarbons, 10.9 mL, 21.8 mmol)in tetrahydrofuran at -78° C. The reaction mixture is stirred at -78° C.for 30 minutes, treated with a solution of3,4,5-trichloro-2-thiophenecarbonitrile (3.87 g, 18.2 mmol) intetrahydrofuran, stirred for 30 minutes at -78° C., warmed to roomtemperature over 45 minutes, quenched with saturated ammonium chloridesolution and extracted with ether. The combined organic extracts arewashed sequentially with water and brine, dried over MgSO₄ andconcentrated in vacuo to obtain a red solid. A mixture of the red solidand 1-bromo-3,3,3-trifluoroacetone (1.95 mL, 18.7 mmol) in acetic acidis refluxed for three hours and 30 minutes, diluted with water andextracted with ether. The combined organic extracts are washedsequentially with water and brine, dried over MgSO₄ and concentrated invacuo to obtain a red solid. Flash chromatography of the solid usingsilica gel and a 15% ethyl acetate in hexane solution gives the titleproduct as a white solid (0.49 g, 7.8%, mp 220°-221° C.).

Using essentially the same procedure, and employing the appropriatelysubstituted cyanofuran or cyanothiophene, the following compounds areobtained:

    ______________________________________                                        A      R     R.sub.1      R.sub.2  mp°C.                               ______________________________________                                         ##STR88##                                                                    S      H     H            H        210                                        S      H     H            Br       230-231                                    S      H     H            Cl       232-233                                    S      H     Br           H        >230                                       O      H     H            H        196-197                                    S      H       CHCHCHCH          >230                                         S      Cl      CHCHCHCH          193-195                                       ##STR89##                                                                    S      H     H            H        229-231                                    ______________________________________                                    

EXAMPLE 5 Preparation of4-Bromo-2-(3,4,5-Trichloro-2-Thienyl)-5-(Trifluoromethyl)Pyrrole-3-Carbonitrile##STR90##

Bromine (0.21 g, 1.31 mmol) is added to a solution of2-(3,4-5-trichloro-2-thienyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile(0.38 g, 1.09 mmol) and sodium acetate (0.11 g, 1.31 mmol) in aceticacid at 50° C. After stirring at 50° C. for 30 minutes, additionalsodium acetate (0.11 g, 1.31 mmol) and bromine (0.208 g, 1.31 mmol) areadded to the reation mixture. The reaction mixture is stirred for 15minutes, cooled to room temperature and poured into a 1% sodiumbisulfite solution. The solids are filtered out of the aqueous mixtureand dried overnight under high vacuum to give a white solid. The solidis recrystallized from ethyl acetate and hexane to obtain the titleproduct as white crystals (0.45 g, 96%, mp 221°-224° C.).

Using essentially the same procedure, and employing the appropriatelysubstituted 2-(thienyl orfuryl)-5-(trifluoromethyl)pyrrole-3-carbonitrile, the followingcompounds are obtained:

    ______________________________________                                        A      R     R.sub.1      R.sub.2  mp°C.                               ______________________________________                                         ##STR91##                                                                    S      H     H            Br       254 (dec.)                                 S      H     H            Cl       >230                                       S      H     Br           Br       >230                                       O      H     H            Br       >230                                       S      Br    CHCHCHCH            201-203                                      S      Cl    CHCHCHCH            205-206                                       ##STR92##                                                                    S      Br    H            H        183-185                                    ______________________________________                                    

EXAMPLE 6 Preparation of4-Bromo-1-(Ethoxymethyl)-2-(3,4,5-Trichloro-2-Thienyl)-5-(Trifluoromethyl)Pyrrole-3-Carbonitrile##STR93##

Chloromethyl ethyl ether (0.20 g, 2.13 mmol) is added to a mixture of4-bromo-2-(3,4,5-trichloro-2-thienyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile(0.30 g, 0.71 mmol) and potassium carbonate (0.29 g, 2.13 mmol) inN,N-dimethylformamide. The reation mixture is stirred at roomtemperature for 30 minutes, diluted with water and extracted with ether.The combined organic extracts are washed sequentially with water andbrine, dried over MgSO₄ and concentrated in vacuo to obtain a clear oil.Flash chromatography of the oil using silica gel and a 15% ethyl acetatein hexane solution gives the title product as white crystals (0 24 g,71%, mp 85°14 87° C.)

Using essentially the same procedure, and employing the appropriatelysubstituted 4-halo-2-(thienyl or furyl) -5- (trifluoromethyl)pyrrole-3-carbonitrile, the following compounds are obtained:

    ______________________________________                                         ##STR94##                                                                    Y      A      R     R.sub.1   R.sub.2 mp°C.                            ______________________________________                                        Cl     S      H     H         H       82-83                                   Br     S      H     H         Br      81-83                                   Br     S      H     H         Cl      81-83                                   Br     O      H     H         Br      80-81                                   Br     S      Br    CHCHCHCH        111-113                                   Br     S      Cl    CHCHCHCH        113-115                                   ______________________________________                                         ##STR95##                                                                    A        R     R.sub.1      R.sub. 2                                                                          mp°C.                                  ______________________________________                                        S        Br    H            H   109-110                                       ______________________________________                                    

EXAMPLE 7 Preparation of4-Chloro-2-(2-Thienyl)-5-(Trifluoromethyl)Pyrrole-3-Carbonitrile##STR96##

Sodium hypochlorite (12 mL of a 5.25% solution, 17 mmol) is addeddropwise to a solution of2-(2-thienyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile (2.00 g, 8.26mmol) in tetrahydrofuran. The reaction mixture is stirred for 2 hoursand 15 minutes, quenched with a 1% sodium bisulfite solution and dilutedwith ether. The layers are separated and the organic layer is washedsequentially with water and brine, dried over MgSO₄ and concentrated invacuo to obtain a yellow solid. Flash chromatography of the solid usingsilica gel and a 15% ethyl acetate in hexane solution gives a solidwhich is recrystallized from ethyl acetate and hexane to obtain thetitle product as a yellow solid (0.35 g, 15%, mp 221°-223° C.).

EXAMPLE 8 Preparation of 5-Bromo-2-Thiophenecarbonitrile ##STR97##

Hydroxylamine-O-sulfonic acid (17.58 g, 157 mmol) is added to a solutionof 5-bromo-2-thiophenecarboxaldehyde (15.00 g, 78.5 mmol) in water andacetonitrile. The reaction mixture is stirred for 17 hours, poured intowater and extracted with ether and ethyl acetate. The combined organicextracts are washed sequentially with water and brine, dried over MgSO₄and concentrated in vacuo to give a brown, oily solid. A solution of theoily solid in acetic anhydride is refluxed for five hours, concentratedin vacuo, poured into water and extracted with ether. The combinedorganic extracts are washed sequentially with water, half-saturatedsodium hydrogen carbonate solution and brine, dried over MgSO₄ andconcentrated in vacuo to obtain a brown oil. Flash chromatography of theoil using silica gel and a 15% ethyl acetate in hexane solution givesthe title product as a yellow oil (3.60 g, 24%).

EXAMPLE 9 Preparation of2-(5-Bromo-2-Furyl)-5-(Trifluoromethyl)Pyrrole-3-Carbonitrile ##STR98##

Bromine (0.71 g, 4.42 mmol) is added to a solution of2-(2-furyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile (1.00 g, 4.42mmol) and sodium acetate (0.36 g, 4.42 mmol) in acetic acid. The reationmixture is stirred for 15 minutes and poured into a 1% sodium bisulfitesolution. The solids are filtered from the aqueous mixture, driedovernight under high vacuum and recrystallized from ethyl acetate andhexane to obtain the title product as red crystals (1.21 g, 90% mp224°-226° C.

Using essentially the same procedure, but substituting2-(2-thienyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile for2-(2-furyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile,2-(2-bromo-3-thienyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile isobtained as a solid, mp 170° C.

EXAMPLE 10 Preparation of2-(5-Formyl-2-Furyl)-5-(Trifluoromethyl)Pyrrole-3-Carbonitrile ##STR99##

Butyllithium (3.45 mL, 7.78 mmol) is added dropwise to a solution of2-(5-bromo-2-furyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile (1.13 g,3.70 mmol) in tetrahydrofuran at -78° C. The reation mixture is stirredat -78° C. for 30 minutes, warmed to room temperature, treated withN,N-dimethylformamide (1.35 g, 18.5 mmol), poured into one molarhydrochloric acid and extracted with ether and ethyl acetate. Thecombined organic extracts are washed sequentially with water and brine,dried over Na₂ SO₄ and concentrated in vacuo to obtain an orange solid.Flash chromatography of the solid using silica gel and 20% to 50% ethylacetate in hexane solutions give an orange solid which is recrystallizedfrom ethyl acetate to obtain the title product as orange crystals (0.66g, 70%, mp 224°-225° C.).

EXAMPLE 11 Preparation of Benzo[b]Thiophene-2-Carboxaldehyde ##STR100##

Butyllithium (54 mL, 134 mmol) is added dropwise to a solution ofN,N,N',N'-tetramethylethylenediamine (15.57 g, 134 mmol) intetrahydrofuran under nitrogen at 0° C. The reaction mixture is treateddropwise with a solution of benzothiophene (15.00 g, 112 mmol) intetrahydrofuran, warmed to room temperature, treated with additionalN,N,N',N'-tetramethylethylenediamine (15.57 g, 134 mmol) andbutyllithium (54 mL, 134 mmol), stirred at room temperature for 13hours, cooled to 0° C. treated with N,N-dimethylformamide (24.40 g, 336mmol), warmed to room temperature, stirred for five hours, poured intoone molar hydrochloric acid and extracted with ether. The combinedorganic extracts are washed sequentially with water and brine, driedover Na₂ SO₄ and concentrated in vacuo to obtain an orange oil. Flashchromatography of the oil using silica gel and a 15% ethyl acetate inhexane solution gives the title product as an orange oil (12.51 g, 69%).

EXAMPLE 12 Preparation of 3-Chlorobenzo[b]Thiophene-2-Carbonitrile##STR101##

Trifluoroacetic anhydride (11.90 g, 56.6 mmol) is added dropwise to amixture of pyridine (5.23 g, 66.1 mmol) and3-chlorobenzo[b]thiophene-2-carboxamide (10.00 g, 47.2 mmol) inmethylene chloride at 0° C. The reaction mixture is warmed to roomtemperature over one hour, diluted with water and extracted with ether.The combined organic extracts are washed sequentially with water, onemolar hydrochloric acid and brine, dried over MgSO₄ and concentrated invacuo to obtain a yellow solid. The solid is recrystallized from ethylacetate and hexane to give the title product as off-white needles (8.80g, 96%).

EXAMPLE 13 Preparation ofβ-[(Formylmethyl)Amino-2-Benzofuranacrylontrile, Diethyl Acetal##STR102##

A mixture of 2-ω-cyanoacetobenzofuran (18.52 g, 100.0 mmol) andaminoacetaldehyde diethyl acetal (14.50 mL, 13.28 g, 99.7 mmol) intoluene is refluxed overnight with removal of water (Dean-Stark trap)and concentrated in vacuo to obtain a black oil. Dry columnchromatography of the oil using silica gel and methylene chloride givesa reddish-black oil. The oil is mixed with a methylene chloride/hexanesolution. The mixture is filtered and the filtrate is concentrated invacuo to obtain the title product as a reddish-black oil, 10.20 g.

EXAMPLE 14 Preparation of 2-(2-Benzofuranyl)Pyrrole-3-Carbonitrile##STR103##

β-[(Formylmethyl)amino]-2-benzofuranacrylonitrile (1.00 g, 3.33 mmol) isadded dropwise to trifluoroacetic acid (5 mL). The reaction mixture isstirred at room temperature for one hour, diluted with water andextracted with ethyl acetate. The organic extract is washed sequentiallywith saturated sodium hydrogen carbonate solution and brine, dried overMgSO₄, decolorized with charcoal and concentrated in vacuo to obtain anorange solid. Dry column chromatography of the solid using silica geland methylene chloride gives the title product as a brown-white solid(0.32 g 46% mp 157°-160.5° C.

EXAMPLE 15 Preparation of4,5-Dichloro-2-(3-Chloro-2-Benzofuranyl)Pyrrole-3-Carbonitrile##STR104##

Sulfuryl chloride (1.20 mL, 2.02 g, 14.9 mmol) is added dropwise to asolution of 2-(2-benzofuranyl)pyrrole-3-carbonitrile (1.00 g, 4.8 mmol)in acetic acid. The reaction mixture is stirred at room temperature for45 minutes and filtered to collect solids. The solids are washed withcold acetic acid and dried overnight to obtain a gray powder. A solutionof the gray powder and tetrahydrofuran is dried over MgSO₄, decolorizedwith charcoal and concentrated in vacuo to give a yellow-white solid. Aslurry of the yellow-white solid and methylene chloride is stirred for90 minutes and filtered to obtain the title product as an off-whitesolid (0.74 g, mp 258°-260.5° C.).

Using essentially the same procedure, but employing two equivalents ofsulfuryl chloride,5-chloro-2-(3-chloro-2-benzofuranyl)pyrrole-3-carbonitrile is obtainedas a white solid, mp 223.5°-225.5° C.

EXAMPLE 16 Preparation of 2-Bromo-1-(5-Chloro-2-Thienyl)Ethanone##STR105##

A solution of bromine (18.90 g, 118 mmol) in chloroform is added to asolution of 2-acetyl-5-chlorothiophene (19.00 g, 118 mmol) in chloroformat 40°-45° C. The reaction mixture is stirred at room temperature fortwo hours and diluted with water. The organic layer is separated, driedover MgSO₄ and concentrated in vacuo to give a solid. The solid isslurried in an ether/hexane solution, filtered and dried to give thetitle product as a solid (12.20 g, mp 68°-70° C.).

EXAMPLE 17 Preparation of [(5-Chloro-2-Thenoyl)Methyl]Malononitrile##STR106##

A solution of 2-bromo-1-(5-chloro-2-thienyl)ethanone (11.50 g, 48 mmol)in tetrahydrofuran is added to a solution of malononitrile (3.17 g, 48mmol) and potassium tert-butoxide (5.70 g, 51 mmol) in tetrahydrofuranat 0° C. The reaction mixture is stirred for several minutes,concentrated in vacuo, diluted with water and filtered to collectsolids. Flash chromatography of the solids using silica gel and a (4:1)hexane/ethyl acetate solution gives the title compound as a yellowsolid, mp 155°-158° C.

EXAMPLE 18 Preparation of2-Chloro-5-(5-Chloro-2-Thienyl)Pyrrole-3-Carbonitrile ##STR107##

Hydrogen chloride gas is bubbled through a mixture of[(5-chloro-2-thenoyl)methyl]malononitrile (4.60 g, 20.5 mmol), ether andchloroform at a moderate rate for 20 minutes. The reaction mixture ispoured into an ice-water mixture and extracted with ether. The combinedorganic extracts are dried over MgSO₄ and concentrated in vacuo to givea brown solid. The solid is mixed with a hexane/ether solution andfiltered to obtain the title product as a brown solid, mp >200° C.

EXAMPLE 19 Preparation of4-Bromo-2-Chloro-5-(5-Chloro-2-Thienyl)Pyrrole-3-Carbonitrile ##STR108##

A solution of bromine (0.70 g, 4.3 mmol) in p-dioxane is added dropwiseto a solution of 2-chloro-5-(5-chloro-2-thienyl)pyrrole-3-carbonitrile(1.00 g, 4.1 mmol) in p-dioxane. The reaction mixture is stirredovernight at room temperature and concentrated in vacuo to obtain aresidue. Flash chromatography of the residue using silica gel and a(6:1) hexane/ethyl acetate solution gives the title product as a yellowsolid, mp >200° C.

EXAMPLE 20 Preparation of4-(p-Chlorophenyl)-2-(Trifluoromethyl)-3-Oxazolin-5-One ##STR109##

A solution of (p-chlorophenyl) glycine (5.05 g, 27.3 mmol) andtrifluoroacetic anhydride (22.90 g, 109.2 mmol) in toluene is refluxedfor five minutes and concentrated in vacuo to obtain the title productas a clear orange oil which is identified by high performance liquidchromatography analysis.

Using essentially the same procedure, but substitutingα-amino-2-thiopheneacetic acid for (p-chlorophenyl)glycine,4-(2-thienyl)-2-(trifluoromethyl)-3-oxazolin-5-one is obtained as abrown oil.

EXAMPLE 21 Preparation of5-(p-Chlorophenyl)-3-(5-Nitro-2-Thienyl)-2-(Trifluoromethyl)Pyrrole##STR110##

Triethylamine (1.16 g, 11.3 mmol) is added to a solution of4-(p-chlorophenyl)-2-(trifluoromethyl)-3-oxazolin-5-one (2.97 g, 11.3mmol) and 2-nitro-5-(2-nitrovinyl)thiophene (2.26 g, 11.3 mmol) inacetonitrile near reflux. The reaction mixture is refluxed for one hour,stirred overnight at room temperature and concentrated in vacuo toobtain a red oil. Chromatography of the oil gives the title product as atan solid, mp 166°-169° C.

Using essentially the same procedure, but substituting2-(2-nitrovinyl)furan for 2-nitro-5-(2-nitrovinyl)thiophene,5-(p-chlorophenyl)-3-(2-furyl)-2-trifluoromethyl)pyrrole is obtained asa tan solid, mp 65°-66° C.

And using essentially the same procedure, but substituting4-(2-thienyl)-2-(trifluoromethyl)-3-oxazolin-5-one for4-(p-chlorophenyl)-2-(trifluoromethyl)-3-oxazolin-5-one and2-chloroacrylonitrile for 2-nitro-5-(2-nitrovinyl)thiophene,2-(2-thienyl)-5-trifluoromethyl)pyrrole-3-carbonitrile is obtained as atan solid, mp 210° C.

EXAMPLE 22 Preparation of2-(p-Chlorophenyl)-3-Nitro-4-(5-Nitro-2-Thienyl)-5-(Trifluoromethyl)Pyrrol##STR111##

A 90% nitric acid solution (0.02 g, 0.28 mmol) is added to a solution of5-(p-chlorophenyl)-3-(5-nitro-2-thienyl)-2-(trifluoromethyl)pyrrole(0.13 g, 0.34 mmol) in acetic anhydride. The reaction mixture is stirredat room temperature for ten minutes, treated with additional 90% nitricacid solution (0.02 g, 0.28 mmol), stirred at room temperature for 15minutes, poured into water, stirred at room temperature overnight andextracted with ether. The combined organic extracts are dried over MgSO₄and concentrated in vacuo to obtain the title product as a tan solidwhich is identified by ¹ HNMR spectral analysis.

EXAMPLE 23 Preparation of4-Bromo-2-(5-Bromo-2-Thienyl)-5-(Trifluoromethyl)Pyrrole-3-Carbonitrileand 4-Bromo-2-[3(or4),5-Dibromo-2-Thienyl]-5-(Trifluoromethyl)Pyrrole-3-Carbonitrile##STR112##

A solution of N-bromosuccinimide (0.84 g, 4.63 mmol) and2-(2-thienyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile (1.02 g, 4.21mmol) in tetrahydrofuran is stirred at room temperature for 20 minutes,treated with additional N-bromosuccinimide (0.84 g, 4.63 mmol), stirredat room temperature for 20 minutes, stirred at reflux for two hours andpoured into water. The aqueous mixture is filtered to obtain solids andfiltrate. A mixture of the solids in toluene is heated, filtered anddried to give4-bromo-2-(5-bromo-2-thienyl)-5-(trifluoromethyl)pyrrole-3-carbonitrileas a solid, mp 254° C. (dec.). The filtrate obtained from the aqueousmixture is concentrated in vacuo and chromatographed using silica geland a (4:1) hexane/ethyl acetate solution to obtain 4-bromo-2-[3(or4),5-dibromo-2-thienyl]-5-(trifluoromethyl)pyrrole-3-carbonitrile as asolid, mp 203° C.

EXAMPLE 24 Preparation of2-[1-(5-Bromo-3-Thienyl)-2-Nitroethyl]-4-(p-Chlorophenyl)-2-(Trifluoromethyl)-3-Oxazolin-5-One##STR113##

A solution of triethylamine (0.30 g, 3 mmol) in toluene is added to asolution of 4-(p-chlorophenyl)-2-(trifluoromethyl)-3-oxazolin-5-one(10.0 g, 38 mmol) and 2-bromo-4-(2-nitrovinyl)thiophene (8.98 g, 32mmol) in toluene at 0° C. The reaction mixture is warmed to roomtemperature and diluted with dilute hydrochloric acid and ether. Theorganic layer is separated, dried over MgSO₄, concentrated in vacuo,diluted with hexane, stirred at reflux, cooled to room temperature anddecanted to obtain a clear solution. The solution is concentrated invacuo and chromatographed to give the title product.

EXAMPLE 25 Preparation of3-(5-Bromo-3-Thienyl)-5-(p-Chlorophenyl)-2-(Trifluoromethyl)Pyrrole and3-(5-Bromo-3-Thienyl)-5-(p-Chlorophenyl)-4-Nitro-2-(Trifluoromethyl)Pyrrole##STR114##

A solution of triethylamine (3.24 g, 32.1 mmol) in acetonitrile is addedslowly to a solution of2-[1-(5-bromo-3-thienyl)-2-nitroethyl]-4-(p-chlorophenyl)-2-(trifluoromethyl)-3-oxazolin-5-one(13.30 g, 26.8 mmol) in acetonitrile. The reaction mixture is stirred atroom temperature for several minutes and diluted with dilutehydrochloric acid. The organic layer is separated, dried over MgSO₄ andconcentrated in vacuo to obtain a black residue. Column chromatographyof the residue using silica gel and a (9:1) hexane/ethyl acetatesolution gives several solids. One of the solids is stirred in cold1,2-dichloroethane, filtered and dried to give3-(5-bromo-3-thienyl)-5-(p-chlorophenyl)-2-(trifluoromethyl)pyrrole as alight tan solid, mp 112°-115° C. Another solid is diluted with hexaneand the mixture is refluxed, cooled to room temperature and filtered toobtain3-(5-bromo-3-thienyl)-5-(p-chlorophenyl)-4-nitro-2-(trifluoromethyl)pyrroleas a yellow solid, mp 174°-176° C.

EXAMPLE 26 Preparation of3-(5-Bromo-4-Nitro-3-Thienyl)-5-(p-Chlorophenyl)-4-Nitro-2-(Trifluoromethyl)Pyrrole)##STR115##

A solution of3-(5-bromo-3-thienyl)-5-(p-chlorophenyl)-2-(trifluoromethyl)pyrrole(0.70 g, 1.7 mmol) and 90% nitric acid (0.145 g, 0.1 mL, 2.1 mmol) inacetic anhydride is stirred at room temperature for 20 minutes, treatedwith additional 90% nitric acid (several drops) and diluted with water.The solids are collected by filtration and dried overnight at 60° C. ina vacuum oven to give the title product as a solid, mp 186°-190° C.

EXAMPLE 27 Preparation of2-(p-Chlorophenyl)-4-(4,5-Dibromo-3-Thienyl)-3-Nitro-5-(Trifluoromethyl)Pyrrole)##STR116##

A solution of3-(5-bromo-3-thienyl)-5-(p-chlorophenyl)-4-nitro-2-(trifluoromethyl)pyrrole(0.50 g, 1.1 mmol), bromine (0.20 g, 1.3 mmol) and sodium acetate (0.11g, 1.3 mmol) in acetic acid (10 mL) is heated overnight at 50° C. andpoured into water. The solids are collected and recrystallized from1,2-dichloroethane to give the title product as a yellow solid, mp241°-242° C.

EXAMPLE 28 Evaluation of In Vitro Fungicidal Activity of Test Compounds

Test compounds are dissolved or suspended in acetone and dispersed intocell well plates containing a suspension of ground fungal mycelia in anutrient broth. Assay plates are incubated for 3-4 days at 21° C. Growthinhibition is measured visually and is rated using the following scale:

    ______________________________________                                        Rating Scale                                                                  Rating      Range % Inhibition                                                ______________________________________                                        0            0                                                                1            1-29                                                             3           30-59                                                             5           60-89                                                             7           90-99                                                             9           100                                                               --          no evaluation                                                     ______________________________________                                    

Untreated controls, solvent blanks and reference standards are includedin each test.

Assay fungi include the plant pathogens, Pythium ultimum (Pythul);Rhizoctonia solani (Rhizso); Fusarium oxysporum f. sp. cucumerinum(Fusoxc); and Pseudocercosporella herpotrichoides (Psdche).

When more than one test is run, the data are averaged. The data obtainedare shown in Table I.

Compounds employed in this in vitro fungicidal evaluation and in the invivo fungicidal evaluation in the following example are given a compoundnumber and identified by name. Data in Table I are reported by compoundnumber.

    ______________________________________                                        COMPOUNDS EVALUATED AS FUNGICIDAL                                             AGENTS                                                                        Compound                                                                      No.                                                                           ______________________________________                                         1         4,5-Dichloro-2-(3-chloro-2-benzofuranyl)-                                     pyrrole-3-carbonitrile                                              2         2-(2-Thienyl)-5-(trifluoromethyl)pyrrole-3-                                   carbonitrile                                                        3         4-Bromo-2-(5-bromo-2-thienyl)-5-(trifluoro-                                   methyl)pyrrole-3-carbonitrile                                       4         5-(p-Chlorophenyl)-3-(2-furyl)-2-(trifluoro-                                  methyl)pyrrole                                                      5         2-(p-Chlorophenyl)-3-nitro-4-(5-nitro-2-                                      thienyl)-5-(trifluoromethyl)pyrrole                                 6         2-Chloro-5-(5-chloro-2-thienyl)pyrrole-3-                                     carbonitrile                                                        7         4-Bromo-2-chloro-5-(5-chloro-2-thienyl)-                                      pyrrole-3-carbonitrile                                              8         3-(5-Bromo-3-thienyl)-5-(p-chlorophenyl)-4-                                   nitro-2-(trifluoromethyl)pyrrole                                    9         3-(5-Bromo-3-thienyl)-5-(p-chlorophenyl)-2-                                   (trifluoromethyl)pyrrole                                           10         2-(p-Chlorophenyl)-4-(4,5-dibromo-3-                                          thienyl)-3-nitro-5-(trifluoromethyl)pyrrole                        11         2-(2-Furyl)-5-(trifluoromethyl)pyrrole-3-                                     carbonitrile                                                       12         4-Chloro-2-(2-thienyl)-5-(trifluoromethyl)-                                   pyrrole-3-carbonitrile                                             13         4-Bromo-2-(5-bromo-2-thienyl)-1-(ethoxy-                                      methyl)-5-(trifluoromethyl)pyrrole-3-                                         carbonitrile                                                       14         2-(5-Bromo-2-furyl)-5-(trifluoromethyl)-                                      pyrrole-3-carbonitrile                                             15         2-(5-Bromo-2-thienyl)-5-(trifluoromethyl)-                                    pyrrole-3-carbonitrile                                             16         2-(5-Chloro-2-thienyl)-5-(trifluoromethyl)-                                   pyrrole-3-carbonitrile                                             17         4-Bromo-2-(5-chloro-2-thienyl)-5-(trifluoro-                                  methyl)pyrrole-3-carbonitrile                                      18         4-Bromo-2-(5-chloro-2-thienyl)-1-(ethoxy-                                     methyl)-5-(trifluoromethyl)pyrrole-3-carbo-                                   nitrile                                                            19         4-Bromo-2-(5-bromo-2-furyl)-5-(trifluoro-                                     methyl)pyrrole-3-carbonitrile                                      20         2-(4-Bromo-2-thienyl)-5-(trifluoromethyl)-                                    pyrrole-3-carbonitrile                                             21         4-Bromo-2-(4,5-dibromo-2-thienyl)-5-(tri-                                     fluoromethyl)pyrrole-3-carbonitrile                                22         4-Bromo-2-(5-bromo-2-furyl)-1-(ethoxy-                                        methyl)-5-(trifluoromethyl)pyrrole-3-carbo-                                   nitrile                                                            ______________________________________                                    

                  TABLE I                                                         ______________________________________                                        In Vitro Fungicidal Evaluations                                               Com-                                                                          pound                                                                         Num-  Rate                                                                    ber   (ppm)   FUSOXC    PSDCHE  PYTHUL  RHIZSO                                ______________________________________                                         1    25      --        1       1       1                                      2    25      --        4       9       4                                      3    25      --        3       8       8                                      4    25      --        9       5       8                                      5    25      3         5       2       7                                      6    25      4         5       8       5                                      7    25      0         4       8       5                                      8    25      0         0       0       3                                      9    25      0         0       0       5                                     10    25      2         0       0       8                                     11    25      0         0       7       4                                     12    25      0         0       7       7                                     13    25      0         0       0       3                                     14    25      0         0       2       3                                     15    25      0         0       0       5                                     16    25      0         0       0       5                                     17    25      0         0       3       5                                     18    25      0         0       0       3                                     19    25      0         0       0       0                                     20    25      0         0       0       0                                     21    25      0         0       0       0                                     22    25      0         0       0       0                                     ______________________________________                                    

EXAMPLE 29 Evaluation of In Vivo Fungicidal Activity of Test Compounds

Test compounds are dissolved or suspended in acetone and diluted withdeionized water containing about 0.05% TWEEN 20®, a polyoxyethylenesorbitan monolaurate surfactant manufactured by Atlas ChemicalIndustries, to give a concentration of 400 ppm or 200 ppm.

Host plants are sprayed with the test solution, dried and inoculatedwith fungi. When disease symptom development is optimal, the plants arerated for disease control according to the rating scale shown below.Each test contains inoculated treated plants, inoculated untreatedplants and a reference standard. When more than one test is run, thedata are averaged. The data obtained are shown in Table II. Thecompounds evaluated are reported by compound number given in example 28.

    ______________________________________                                        Rating Scale                                                                  Rating      Range % Control                                                   ______________________________________                                        0            0                                                                1            1-14                                                             2           15-29                                                             3           30-44                                                             4           45-59                                                             5           60-74                                                             6           75-89                                                             7           90-95                                                             8           96-99                                                             9           100                                                               --          no evaluation                                                     ______________________________________                                        PHYTOPATHOGENIC FUNGI                                                         Symbol   Disease          Pathogen                                            ______________________________________                                        AS       Apple Scab       Venturia inaegualis                                 GDM      Grape Downy Mildew                                                                             Plasmopara viticola                                 PB       Pepper Botrytis  Botrytis cinerea                                    RB       Rice Blast       Pyricularia oryzae                                  SBC      Sugar Beet Cercospora                                                                          Cercospora beticola                                 WLR      Wheat Leaf Rust  Puccinia recondita                                                            f. sp. tritici                                      WPM      Wheat Powdery Mildew                                                                           Erysiphe graminis                                                             f. sp. tritici                                      ______________________________________                                    

                  TABLE II                                                        ______________________________________                                        In Vivo Fungicidal Evaluations                                                Com-                                                                          pound                                                                         Num-  Rate                                                                    ber   (ppm)   AS     GDM   PB  RB   SBC  WLR   WPM                            ______________________________________                                        1     400     0      --    2   4    0    2     0                              2     400     9      9     --  5    0    9     9                              3     400     9      9     --  0    --   9     7                              4     400     2      8     0   1    0    6     0                              5     400     4      9     0   0    --   6     0                              6     400     9      7     0   0    6    6     0                              7     400     8      0     0   0    0    7     0                              8     400     8      9     0   4    --   7     0                              9     400     0      6     0   0    0    0     0                              10    400     0      7     0   7    0    --    4                              11    200     0      0     0   0    0    --    --                             12    200     4      8     0   0    0    --    8                              13    200     0      0     0   0    0    --    9                              14    200     0      6     0   0    0    --    6                              ______________________________________                                    

What is claimed is:
 1. A method for control or amelioration of a diseasecaused by a phytopathogenic fungus which comprises contacting saidfungus with a fungicidally effective amount of a compound having thestructural formula ##STR117## wherein R, R₁ and R₂ are eachindependently hydrogen, halogen, NO₂ or CHO, and when R₁ and R₂ aretaken together with the carbon atoms to which they are attached, theymay form a ring in which R₁ R₂ is represented by the structure:##STR118## L, T, V and W are each independently hydrogen, halogen, CN orNO₂ ; A is S;X is CN, NO₂, C₁ -C₆ haloalkyl, S(O)_(m) CF₂ R₃ or C(S)NR₄R₅ ; R₃ is hydrogen, F, Cl, Br, C CCl₃ ; m is an integer of 0, 1 or 2;R₄ and R₅ are each independently hydrogen,C₁ -C₄ alkyl optionallysubstituted with one or more halogen atoms, or phenyl optionallysubstituted with one or more halogen atoms,NO₂ groups, CN groups, C₁ -C₄alkyl groups optionally substituted with one or more halogen atoms, orC₁ -C₄ alkoxy groups optionally substituted with one or more halogenatoms; Y is hydrogen, halogen, C₁ -C₆ haloalkyl, S(O)_(m) CF₂ R₃, CNorphenyl optionally substituted with one or more halogen atoms,NO₂groups, CN groups, C₁ -C₄ alkyl groups optionally substituted with oneor more halogen atoms, or Cl-C₄ alkoxy groups optionally substitutedwith one or more halogen atoms; Z is hydrogen, halogen or C₁ -C₆haloalkyl; B is R₆, OR₆ or CN; R₆ is hydrogen, C(O)R₇, CHR₈ NHC(O)R₉,CH₂ SQ, CHR₁₀ OC(O) (CR₁₁ R₁₂)_(n) Q₁,C₁ -C₆ alkyl optionallysubstituted with one to three halogen atoms,one tri(C₁ -C₄ alkyl)silyl,one hydroxy, one cyano, one or two C₁ -C₄ alkoxy groups optionallysubstituted with one to three halogen atoms, one C₁ -C₄ alkylthio, onephenyl optionally substituted with one to three halogen atoms, one tothree C₁ -C₄ alkyl groups or one to three C₁ -C₄ alkoxy groups, onephenoxy group optionally substituted with one to three halogen atoms,one to three C₁ -C₄ alkyl groups or one to three C₁ -C₄ alkoxy groups,one benzyloxy group optionally substituted on the phenyl ring with oneto three halogen atoms, one to three C₁ -C₄ alkyl groups or one to threeC₁ -C₄ alkoxy groups, one C₁ -C₆ alkylcarbonyloxy group optionallysubstituted with one to three halogen atoms, one C₂ -C₆alkenylcarbonyloxy group optionally substituted with one to threehalogen atoms, one phenylcarbonyloxy group optionally substituted withone to three halogen atoms, one to three C₁ -C₄ alkyl groups or one tothree C₁ -C₄ alkoxy groups, one C₁ -C₆ alkoxycarbonyl group optionallysubstituted with one to three halogen atoms or one to three C₁ -C₄alkoxy groups, or one benzylcarbonyloxy group optionally substituted onthe phenyl ring with one to three halogen atoms, one to three C₁ -C₄alkyl groups or one to three C₁ -C₄ alkoxy groups, C₃ -C₆ alkenyloptionally substituted with one to three halogen atoms or one phenylgroup, or C₃ -C₆ alkynyl optionally substituted with one to threehalogen atoms or one phenyl group; R₇ is C₁ -C₆ alkyl or C₃ -C₆cycloalkyl each optionally substituted with one to three halogenatoms,one hydroxy, one cyano, one or two C₁ -C₄ alkoxy groups optionallysubstituted with one to three halogen atoms, one C₁ -C₄ alkylthio, onephenyl group optionally substituted with one to three halogen atoms, oneto three C₁ -C₄ alkyl groups or one to three C₁ -C₄ alkoxy groups, onephenoxy group optionally substituted with one to three halogen atoms,one to three C₁ -C₄ alkyl groups or one to three C₁ -C₄ alkoxy groups,one benzyloxy group optionally substituted on the phenyl ring with oneto three halogen atoms, one to three C₁ -C₄ alkyl groups or one to threeC₁ -C₄ alkoxy groups, one C₁ -C₆ alkylcarbonyloxy group optionallysubstituted with one to three halogen atoms, one C₂ -C₆alkenylcarbonyloxy group optionally substituted with one to threehalogen atoms, one phenylcarbonyloxy group optionally substituted withone to three halogen atoms, one to three C₁ -C₄ alkyl groups or one tothree C₁ -C₄ alkoxy groups, one C₁ -C₆ alkoxycarbonyl group optionallysubstituted with one to three halogen atoms or one to three C₁ -C₄alkoxy groups, or one benzyloxycarbonyl group optionally substituted onthe phenyl ring with one to three halogen atoms, one to three C₁ -C₄alkyl groups or one to three C₁ -C₄ alkoxy groups, C₂ -C₆ alkenyloptionally substituted with one to three halogen atoms or one phenylgroups, C₃ -C₆ alkynyl optionally substituted with one to three halogenatoms or one phenyl group, phenyl optionally substituted with one ormore halogen atoms, C₁ -C₄ alkyl groups, C₁ -C₄ alkoxy groups, phenoxygroups, C₁ -C₄ alkylthio groups, tri(C₁ -C₄ alkyl)silyl groups, C₁ -C₄alkylsulfinyl groups, C₁ -C₄ alkylsulfonyl groups, CN groups, NO₂ groupsor CF₃ groups, phenoxy optionally substituted with one or more halogenatoms, C₁ -C₄ alkyl groups, C₁ -C₄ alkoxy groups, C₁ -C₄ alkylthiogroups, tri(C₁ -C₄ alkyl)silyl groups, C₁ -C₄ alkylsulfinyl groups, C₁-C₄ alkylsulfonyl groups, CN groups, NO₂ groups or CF₃ groups, 1- or2-naphthyl, 2-, 3-, or 4-pyridyl optionally substituted with one tothree halogen atoms, C₁ -C₆ alkoxy optionally substituted with one tothree halogen atoms, or C₂ -C₆ alkenyloxy optionally substituted withone to three halogen atoms; R₈ is hydrogen or C₁ -C₄ alkyl; R₉ is C₁ -C₆alkyl optionally substituted with one to three halogen atoms,phenyloptionally substituted with one to three halogen atoms, CN groups, NO₂groups, C₁ -C₄ alkyl groups, C₁ -C₄ alkoxy groups or CF₃ groups, 2- or3-thienyl, or 2- or 3-furyl; Q is ##STR119## CN, C₁ -C₆ alkyl optionallysubstituted with one or more halogen atoms, CN groups or phenyl groups,orphenyl optionally substituted with one or more halogen atoms, C₁ -C₄alkyl groups, C₁ -C₄ alkoxy groups, CN groups, NO₂ groups, CF₃ groups orNR₂₄ R₂₅ groups; A₁ is O or S; R₁₃ is C₁ -C₆ alkyl or phenyl; R₁₄ is C₁-C₆ alkyl; R₁₅ and R₁₆ are each independently hydrogen, C₁ -C₆ alkyl ormay be taken together with the atom to which they are attached to form a5- to 7-membered ring; R₁₇ is C₁ -C₄ alkyl; R₁₈ is hydrogen, C₁ -C₄alkyl or may be taken together with either R₁₉ or R₂₁ and the atoms towhich they are attached to form a 5- to 7-membered ring optionallysubstituted with one or two C₁ -C₄ alkyl groups; R₁₉ and R₂₀ are eachindependently hydrogen or C₁ -C₄ alkyl; R₂₁ is C₁ -C₄ alkyl or whentaken together with R₁₈ and the atoms to which they are attached mayform a 5- to 7-membered ring optionally substituted with one or two C₁-C₄ alkyl groups; R₂₂ and R₂₃ are each independently hydrogen or C₁ -C₄alkyl or when taken together may form a ring wherein R₂₂ R₂₃ isrepresented by --CH═CH--CH═CH--; R₂₄ and R₂₅ are each independentlyhydrogen or C₁ -C₄ alkyl; R₁₀ is hydrogen or C₁ -C₄ alkyl; R₁₁ and R₁₂are each independently hydrogen,C₁ -C₆ alkyl optionally substituted withone or more halogen atoms, C₁ -C₆ alkoxy optionally substituted with oneor more halogen atoms, C₁ -C₆ alkylthio optionally substituted with oneor more halogen atoms, or phenyl optionally substituted with one or morehalogen atoms,NO₂ groups; CN groups, C₁ -C₄ alkyl groups optionallysubstituted with one or more halogen atoms, or C₁ -C₄ alkoxy groupsoptionally substituted with one or more halogen atoms, or when R₁₁ andR₁₂ are taken together with the atom to which they are attached may forma C₃ -C₆ cycloalkyl group optionally substituted with one to three C₁-C₄ alkyl groups, C₂ -C₆ alkenyl groups or phenyl groups, or R₁₁ or R₁₂may be taken together with R₂₆ and the atoms to which they are attachedto form a 4- to 7-membered heterocyclic ring; n is an integer of 0, 1,2, 3 or 4; Q₁ is A₂ R₂₆, ##STR120## NR₂₈ R₂₉, CR₃₀ R₃₁ C(O)R₃₂, or C₃-C₆ cycloalkyl optionally substituted with one or more C₁ -C₆ alkylgroups,C₂ -C₆ alkenyl groups, or phenyl groups optionally substitutedwith one or more halogen atoms,NO₂ groups, CN groups, C₁ -C₄ alkylgroups optionally substituted with one or more halogen atoms, or C₁ -C₄alkoxy groups optionally substituted with one or more halogen atoms; A₂is O or S(O)_(p) ; p is an integer of 0, 1 or 2; R₂₆ is hydrogen,C₁ -C₆alkyl C₂ -C₆ alkenyl, C₂ -C₆ alkynyl, phenyl optionally substituted withone or more halogen atoms,NO₂ groups, CN groups, C₁ -C₄ alkyl groupsoptionally substituted with one or more halogen atoms, C₁ -C₄ alkoxygroups optionally substituted with one or more halogen atoms, C(O)R₃₃provided p is O, C(O)R₃₄ provided p is O, (CH₂ CH₂ O)_(q) R₃₃, or##STR121## R₂₆ may be taken together with either R₁₁ or R₁₂ and theatoms to which they are attached to form a 4- to 7-membered heterocyclicring; A₃ is O or S; R₃₃ is C₁ -C₆ alkyl,C₂ -C₆ alkenyl, C₂ -C₆ alkynyl,or phenyl optionally substituted with one or more halogen atoms,NO₂groups, CN groups, C₁ -C₄ alkyl groups optionally substituted with oneor more halogen atoms, or C₁ -C₄ alkoxy groups optionally substitutedwith one or more halogen atoms; q is an integer of 1, 2 or 3; R₃₄ isOR₃₇ or NR₃₈ R₃₉ ; R₃₇ is C₁ -C₆ alkyl or phenyl optionally substitutedwith one or more halogen atoms,NO₂ groups, CN groups, C₁ --C₄ alkylgroups optionally substituted with one or more halogen atoms, or C₁ -C₄alkoxy groups optionally substituted with one or more halogen atoms; R₃₈and R₃₉ are each independently hydrogen or C₁ -C₄ alkyl; R₃₅ and R₃₆ areeach independently hydrogen or C₁ -C₄ alkyl, or when taken together mayform a ring wherein R₃₅ R₃₆ is represented by --CH═CH--CH═CH--; R₂₇ isC₁ -C₄ alkyl; R₂₈ is hydrogen,C₁ -C₆ alkyl, C₂ -C₆ alkenyl, C₂ -C₆alkynyl, or phenyl optionally substituted with one or more halogenatoms,NO₂ groups, CN groups, C₁ --C₄ alkyl groups optionally substitutedwith one or more halogen atoms, or C₁ -C₄ alkoxy groups optionallysubstituted with one or more halogen atoms, or R₂₈ may be taken togetherwith either R₁₁ or R₁₂ and the atoms to which they are attached to forma 4- to 7-membered heterocyclic ring; R₂₉ is hydrogen,C₁ -C₆ alkyl, C₂-C₆ alkenyl, C₂ -C₆ alkynyl, phenyl optionally substituted with one ormore halogen atoms,NO₂ groups, CN groups, C₁ -C₄ alkyl groups optionallysubstituted with one or more halogen atoms, or C₁ -C₄ alkoxy groupsoptionally substituted with one or more halogen atoms, C(A₄)R₄₀, CN, SO₂R₄₁, or C(O)CHR₄₂ NHR₄₃ ; A₄ is O or S; R₄₀ is OR₄₄, CO₂ R₄₄, NR₄₅R₄₆,C₁ -C₆ alkyl optionally substituted with one to three halogen atoms,C₂ -C₆ alkenyl, C₂ -C₆ alkynyl, or phenyl optionally substituted withone or more halogen atoms,NO₂ groups, CN groups, C₁ -C₄ alkyl groupsoptionally substituted with one or more halogen atoms, or C₁ -C₄ alkoxygroups optionally substituted with one or more halogen atoms; R₄₄ is C₁-C₆ alkyl optionally substituted with one phenyl group, orphenyloptionally substituted with one or more halogen atoms,NO₂ groups, CNgroups, C₁ -C₄ alkyl groups optionally substituted with one or morehalogen atoms, or C₁ -C₄ alkoxy groups optionally substituted with oneor more halogen atoms; R₄₅ and R₄₆ are each independently hydrogen or C₁-C₄ alkyl; R₄₁ is NR₄₇ R₄₈,C₁ -C₆ alkyl, C₂ -C₆ alkenyl, C₂ -C₆ alkynyl,or phenyl optionally substituted with one or more halogen atoms,NO₂groups, CN groups, C₁ -C₄ alkyl groups optionally substituted with oneor more halogen atoms, or C₁ -C₄ alkoxy groups optionally substitutedwith one or more halogen atoms; R₄₇ and R₄₈ are each independentlyhydrogen or C₁ -C₄ alkyl; R₄₂ is hydrogen,C₁ -C₄ alkyl optionallysubstituted with one hydroxy group,one SR₄₉ group, one C(O)NH₂ group,one NH₂ group, one NHC(═NH)NH₂ group, one CO₂ H group, one phenyl groupoptionally substituted with one hydroxy group, one 3-indolyl group orone 4-imidazolyl group; R₄₉ is hydrogen or C₁ -C₄ alkyl; R₄₃ is C(A₄)R₅₀; R₅₀ is C₁ -C₆ alkyl optionally substituted with one or more halogenatoms,C₁ -C₆ alkoxyalkyl, C₁ -C₆ alkylthio, phenyl optionallysubstituted with one or more halogen atoms,NO₂ groups, CN groups, C₁ -C₄alkyl groups optionally substituted with one or more halogen atoms, orC₁ -C₄ alkoxy groups optionally substituted with one or more halogenatoms, OR₄₄, CO₂ R₄₄ or NR₄₅ R₄₆ ; R₃₀ and R₃₁ are each independentlyhydrogen,C₁ -C₆ alkyl optionally substituted with one or more halogenatoms, C₁ -C₆ alkoxy optionally substituted with one or more halogenatoms, C₁ -C₆ alkylthio optionally substituted with one or more halogenatoms, phenyl optionally substituted with one or more halogen atoms,CNgroups, NO₂ groups, C₁ -C₄ alkyl groups optionally substituted with oneor more halogen atoms, or C₁ -C₄ alkoxy groups optionally substitutedwith one or more halogen atoms, or when R₃₀ and R₃₁ are taken togetherwith the atom to which they are attached may form a C₃ -C₆ cycloalkylgroup optionally substituted with one to three C₁ -C₄ alkyl groups, C₂-C₆ alkenyl groups or phenyl groups; R₃₂ is OR₅₁, NR₄₇ R₄₈, C₁ -C₄ alkylor phenyl optionally substituted with one or more halogen atoms,CNgroups, NO₂ groups, C₁ -C₄ alkyl groups optionally substituted with oneor more halogen atoms, or C₁ -C₄ alkoxy groups optionally substitutedwith one or more halogen atoms; and R₅₁ is C₁ -C₄ alkyl or phenyloptionally substituted with one or more halogen atoms,CN groups, NO₂groups, C₁ -C₄ alkyl groups optionally substituted with one or morehalogen atoms, or C₁ -C₄ alkoxy groups optionally substituted with oneor more halogen atoms;provided that when X is S(O)_(m) CF₂ R₃ and Z ishydrogen, then Y is hydrogen, halogen, C₁ -C₆ haloalkyl, S(O)_(m) CF₂ R₃or CN; and further provided that when the pyrrole ring is substitutedwith hydrogen at each of the pyrrole carbon atoms adjacent to the ringnitrogen atom, then X cannot be CN or NO₂.
 2. The method according toclaim 1 whereinR, R₁ and R₂ are each independently hydrogen, halogen orNO₂, and when R₁ and R₂ are taken together with the carbon atoms towhich they are attached, they may form a ring in which R₁ R₂ isrepresented by the structure: ##STR122## L, T, V and W are eachindependently hydrogen, halogen, CN or NO₂ ; A is S; X is CN, NO₂, C₁-C₆ haloalkyl, S(O)_(m) CF₂ R₃ or C(S)NR₄ R₅ ; R₃ is hydrogen, F, Cl,Br, CF₂ H, CCl₂ H, CClFH, CF₃ or CCl₃ ; m is an integer of 0, 1 or 2; R₄and R₅ are each independently hydrogen,C₁ -C₄ alkyl optionallysubstituted with one or more halogen atoms or phenyl optionallysubstituted with one or more halogen atoms,NO₂ groups, CN groups, C₁ -C₄alkyl groups optionally substituted with one or more halogen atoms, orC₁ -C₄ alkoxy groups optionally substituted with one or more halogenatoms; Y is hydrogen, halogen, C₁ -C₆ haloalkyl, S(O)_(m) CF₂ R₃, CNorphenyl optionally substituted with one or more halogen atoms,NO₂groups, CN groups, C₁ -C₄ alkyl groups optionally substituted with oneor more halogen atoms, or C₁ -C₄ alkoxy groups optionally substitutedwith one or more halogen atoms; Z is hydrogen, halogen or C₁ -C₆haloalkyl; B is R₆ or CN; R₆ is hydrogen, C(O)₇ orC₁ -C₆ alkyloptionally substituted with one to three halogen atoms,one cyano, one C₁-C₄ alkoxy group, one C₁ -C₆ alkylcarbonyloxy group, onephenylcarbonyloxy group, or one benzylcarbonyloxy groups; and R₇ isphenyl optionally substituted with one or more halogen atoms, C₁ -C₄alkyl groups, C₁ -C₄ alkoxy groups, CN groups, NO₂ groups or CF₃ groups.3. The method according to claim 2 whereinR, R₁ and R₂ are eachindependently hydrogen, halogen or NO₂, and when R₁ and R₂ are takentogether with the carbon atoms to which they are attached, they may forma ring in which R₁ R₂ is represented by the structure: ##STR123## L, T,V and W are each independently hydrogen, halogen, CN or NO₂ ; A is or S;X is CN, NO₂ or C₁ -C₆ haloalkyl; Y is hydrogen, halogen, C₁ -C₆haloalkyl or phenyl optionally substituted with one or more halogenatoms,NO₂ groups, CN groups, C₁ -C₄ alkyl groups optionally substitutedwith one or more halogen atoms, or C₁ -C₄ alkoxy groups optionallysubstituted with one or more halogen atoms; Z is hydrogen, halogen or C₁-C₆ haloalkyl; B is R₆ or CN; R₆ is hydrogen, C(O)R₇ or C₁ -C₆ alkyloptionally substituted with one to three halogen atoms,one cyano, one C₁-C₄ alkoxy group, one C₁ -C₆ alkylcarbonyloxy group, onephenylcarbonyloxy group, or one benzylcarbonyloxy group; and R₇ isphenyl optionally substituted with one or more halogen atoms, C₁ -C₄alkyl groups, C₁ -C₄ alkoxy groups, CN groups, NO₂ groups or CF₃ groups.4. The method according to claim 3 whereinR, R₁ and R₂ are eachindependently hydrogen, halogen or NO₂, and when R₁ and R₂ are takentogether with the carbon atoms to which they are attached, they may forma ring in which R₁ R₂ is represented by the structure: ##STR124## L, T,V and W are each independently hydrogen, halogen, CN or NO₂ ; A is S; Xis CN, NO₂ or C₁ -C₆ haloalkyl; Y is hydrogen, halogen, C₁ -C₆ haloalkylor phenyl optionally substituted with one or more halogen atoms,NO₂groups, CN groups, C₁ -C₄ alkyl groups optionally substituted with oneor more halogen atoms, or C₁ -C₄ alkoxy groups optionally substitutedwith one or more halogen atoms; Z is halogen or C₁ -C₆ haloalkyl; B isR₆ or CN; R₆ is hydrogen, C(O)R₇ or C₁ -C₆ alkyl optionally substitutedwith one to three halogen atoms,one cyano, one C₁ -C₄ alkoxy group, oneC₁ -C₆ alkylcarbonyloxy group, one phenylcarbonyloxy group, or onebenzylcarbonyloxy group; and R₇ is phenyl optionally substituted withone or more halogen atoms, C₁ -C₄ alkyl groups, C₁ -C₄ alkoxy groups, CNgroups, NO₂ groups or CF₃ groups.
 5. The method according to claim 3whereinR, R₁ and R₂ are each independently hydrogen, halogen or NO₂, andwhen R₁ and R₂ are taken together with the carbon atoms to which theyare attached, they may form a ring in which R₁ R₂ is represented by thestructure:

    --CH═CH--CH═CH--;

A is S; X is CN or NO₂ ; Y is halogen, CF₃ or phenyl optionallysubstituted with one or more halogen atoms,NO₂ groups, CN groups, C₁ -C₄alkyl groups optionally substituted with one or more halogen atoms, orC₁ -C₄ alkoxy groups optionally substituted with one or more halogenatoms; Z is hydrogen, halogen or CF₃ ; and B is hydrogen or C₁ -C₆ alkylsubstituted with one C₁ -C₄ alkoxy group.
 6. The method according toclaim 5 whereinR, R₁ and R₂ are each independently hydrogen, halogen orNO₂ ; A is S; X is CN or NO₂ ; Y is halogen, CF₃ or phenyl optionallysubstituted with one or more halogen atoms,NO₂ groups, CN Groups, C₁ -C₄alkyl groups optionally substituted with one or more halogen atoms, orC₁ -C₄ alkoxy groups optionally substituted with one or more halogenatoms; Z is CF₃ ; and B is hydrogen or C₁ -C₆ alkyl substituted with oneC₁ -C₄ alkoxy group.
 7. The method according to claim 5 wherein thecompound is selected from the group consistingof2-(2-thienyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile;4-bromo-2-(5-bromo-2-thienyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile;3-(5-bromo-3-thienyl)-5-(p-chlorophenyl)-4-nitro-2-(trifluoromethyl)pyrrole2-chloro-5-(5-chloro-2-thienyl)pyrrole-3-carbonitrile; and2-(p-chlorophenyl)-3-nitro-4-(5-nitro-2-thienyl)-5-(trifluoromethyl)pyrrole.8. The method according to claim 1 wherein the compound is applied at aconcentration of about 20 ppm to 1,000 ppm.
 9. A method for theprotection of a plant, plant seed or tuber from fungal infestation anddisease which comprises applying to the plant, plant seed or tuber, orto the medium or water in which it is growing, a fungicidally effectiveamount of a compound having the structural formula ##STR125## wherein R,R₁, R₂, A, X, Y, Z and B are as described in claim
 1. 10. The methodaccording to claim 9 wherein R, R₁, R₂, A, X, Y, Z and B are asdescribed in claim
 2. 11. The method according to claim 10 wherein R,R₁, R₂, A, X, Y, Z and B are as described in claim
 3. 12. The methodaccording to claim 11 wherein R, R₁, R₂, A, X, Y, Z and B are asdescribed in claim
 4. 13. The method according to claim 11 wherein R, R₁and R₂ are each independently hydrogen, halogen or NO₂, and when R₁ andR₂ are taken together with the carbon atoms to which they are attached,they may form a ring in which R₁ R₂ is represented by the structure:

    --CH═CH--CH═CH--;

A is S; X is CN or NO₂ ; Y is halogen, CF₃ or phenyl optionallysubstituted with one or more halogen atoms,NO₂ groups, CN groups, C₁ -C₄alkyl groups optionally substituted with one or more halogen atoms, orC₁ -C₄ alkoxy groups optionally substituted with one or more halogenatoms; Z is hydrogen, halogen or CF₃ ; and B is hydrogen or C₁ -C₆ alkylsubstituted with one C₁ -C₄ alkoxy group.
 14. The method according toclaim 13 wherein R, R₁ and R₂ are each independently hydrogen, halogenor NO₂ ;A is S; X is CN or NO₂ ; Y is halogen, CF₃ or phenyl optionallysubstituted with one or more halogen atoms,NO₂ groups, CN groups, C₁ -C₄alkyl groups optionally substituted with one or more halogen atoms, orC₁ -C₄ alkoxy groups optionally substituted with one or more halogenatoms; Z is CF₃ ; and B is hydrogen or C₁ -C₆ alkyl substituted wtih oneC₁ -C₄ alkoxy group.
 15. The method according to claim 13 wherein thecompound is selected from the group consistingof2-(2-thienyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile;4-bromo-2-(5-bromo-2-thienyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile;3-(5-bromo-3-thienyl)-5-(p-chlorophenyl)-4-nitro-2-(trifluoromethyl)pyrrole;2-chloro-5-(5-chloro-2-thienyl)pyrrole-3-carbonitrile; and2-(p-chlorophenyl)-3-nitro-4-(5-nitro-2-thienyl)-5-(trifluoromethyl)pyrrole.16. A composition for controlling phytopathogenic fungi which comprisesan inert liquid or solid carrier and a fungicidally effective amount ofa compound having the structural formula ##STR126## wherein R, R₁, R₂,A, X, Y, Z and B are as described in claim
 1. 17. The compositionaccording to claim 16 wherein R, R₁, R₂, A, X, Y, Z and B are asdescribed in claim
 2. 18. The composition according to claim 17 whereinR, R₁, R₂, A, X, Y, Z and B are as described in claim
 3. 19. Thecomposition according to claim 18 wherein R, R₁, R₂, A, X, Y, Z and Bare as described in claim
 4. 20. The composition according to claim 18whereinR, R₁ and R₂ are each independently hydrogen, halogen or NO₂, andwhen R₁ and R₂ are taken together with the carbon atoms to which theyare attached, they may form a ring in which R₁ R₂ is represented by thestructure: --CH═CH--CH═CH--; A is S; X is CN or NO₂ ; Y is halogen, CF₃or phenyl optionally substituted with one or more halogen atoms,NO₂groups, CN groups, C₁ -C₄ alkyl groups optionally substituted with oneor more halogen atoms, or C₁ -C₄ alkoxy groups optionally substitutedwith one or more halogen atoms; Z is hydrogen, halogen or CF₃ ; and B ishydrogen or C₁ -C₆ alkyl substituted with one C₁ -C₄ alkoxy group.